James began taking apart electronics gear as a teenager growing up in Cornwall, England. (If the title Selected Ambient Works 85-92 is to be believed, it contains recordings made at the age of 14.) Inspired by acid-house in the late '80s, James began DJing raves around Cornwall. His first release was the Analogue Bubblebath EP, recorded with Tom Middleton and released on the Mighty Force label in September 1991. Middleton left later that year to form Global Communication, after which James recorded a second volume in the Analogue Bubblebath series. This EP (the first to include "Digeridoo") got some airplay on the London pirate radio-station Kiss FM, and prompted Belgium's R&S Records to sign him early the following year. A re-recording of "Digeridoo" made number 55 in the British charts just after its April 1992 release date, and James followed with the Xylem Tube EP in June. He also co-formed (with Grant Wilson-Claridge) his own Rephlex label around that time, releasing a series of singles as Caustic Window during 1992-93. Available in cruelly limited editions, most of the recordings continued the cold acid precision of "Digeridoo" -- though several expressed humor and fragility barely dreamed of in the hardcore/rave scene to that point.

The climate for "intelligent" techno had begun to warm in the early '90s, though. The Orb had proved the commercial viability of ambient-house with their chart-topping "Blue Room" single, and R&S scrambled to find useful material from its own artists. In November 1992, James acquiesced with Selected Ambient Works 85-92, consisting mostly of home material recorded during the past few years. Simply stated, it was a masterpiece of ambient-techno, the genre's second work of brilliance after The Orb's Adventures Beyond the Ultraworld. As his star began to shine, several bands approached him to remix their work, and he complied, with mostly unrecognizable reworkings of tracks by St. Etienne, the Cure, Jesus Jones, Meat Beat Manifesto and Curve.

Early in 1993, Richard James signed to Warp Records, the influential British label that virtually introduced the concept of futuristic "electronic listening music" with a series of albums (sub-titled Artificial Intelligence) by ambient-techno pioneers Black Dog, Autechre, B12 and FUSE (aka Richie Hawtin) among others. James' release in the series, titled Surfing on Sine Waves, was recorded as Polygon Window and released in January 1993. The album charted a course between the raw muscle of James' nose-bleed techno and the understated minimalism of Selected Ambient Works. A deal between Warp and TVT gave Surfing on Sine Waves an American release (James' first) by the summer. A second album was released that year, Analogue Bubblebath 3, for Rephlex. Recorded as AFX, the LP renounced any debt to ambient music and was the most bracing work yet in the Aphex Twin canon. On a tour of America with Orbital and Moby later that year, James clung to the head-banging material, to the detriment of his mostly unreplaceable gear. He later cut down on his live-performance schedule.

In December of 1993, the new single "On" resulted in James' highest chart placing, a number 32 spot on the British charts. The two-part single included remixes by old pal Tom Middleton (as Reload) and future Rephlex star µ-Ziq. Despite James' appearance on the pop charts, his following album Selected Ambient Works, Vol. 2 appeared to be a joke on the ambient-techno community. So minimal as to be barely conscious, the quadruple-album left most of the beats behind, with only tape loops of unsettling ambient noise remaining. The album mostly struck out with critics, but hit number 11 on the British charts and earned James a major-label American contract with Sire soon after. During 1994, he worked on the ever-growing Rephlex stable, signing µ-Ziq (Michael Paradinas), Kosmik Kommando (Mike Dred), and Kinesthesia/Cylob (Chris Jeffs) to the label. In August 1994, he released the fourth Analogue Bubblebath, this one a five-track EP.

The year 1995 began with the January release of Classics, a compilation of his early R&S singles. Two months later, James released the single "Ventolin," a harsh, appropriately wheezing ode to the asthma drug on which he relied. I Care Because You Do followed in April, pairing his hardcore experimentalism with more symphonic ambient material, aligned with the work of many post-classical composers -- including Philip Glass, who arranged an orchestral version of the album's "Icct Hedral" on the August 1995 single, "Donkey Rhubarb."

Later that year, the Hangable Auto Bulb EP replaced Analogue Bubblebath 3 as Aphex Twin's most brutal, uncompromising release -- a fusion of experimental music and jungle being explored at the same time on releases by Plug and Squarepusher. In July 1996, Rephlex released the long-awaited collaboration beween Richard James and Michael Paradinas (µ-Ziq). The album, Expert Knob Twiddlers (credited to Mike & Rich) watered down the experimentalism of Aphex Twin with µ-Ziq's easy-listening electro-funk. The fourth proper Aphex Twin album, November 1996's Richard D. James Album, continued his forays into acid-jungle and experimental music. Retaining the experimental edge, but with a stated wish to make the British pop charts, James' next two releases, the EPs Come to Daddy and Windowlicker, were acid storms of industrial drum'n'bass. The accompanying videos, both directed by Chris Cunningham, featured the bodies of small children and models (respectively) dancing around, all with special-effects-created Aphex Twin faces grinning maniacally.