During this period, she was considered the strongest female sport climber in the world along with Lynn Hill, however, in 1990 she retired to focus on alpine climbing.

From 1992 to 1994, Destivelle became the first female to complete the winter alpine free solo of the "north face trilogy" of the Eiger, the Grandes Jorasses, and the Matterhorn.

[2][4] Destivelle recovered and in 1986 set new records by becoming the first female to climb an 8a (5.13b) route with Fleur de Rocaille (later downgraded to 7c+/8a), and winning again at Sportroccia, beating her main rival Lynn Hill.

[2][5][8] 1988 would be the pinnacle of Destivelle's sport climbing career when she redpointed Choucas in Buoux, the first female ascent of an 8a+ (5.13c) graded route.

Her 11-day free solo of the route, which bears her name in her honor, was captured in the film 11 Days on the Dru, and covered widely in the international media.

[4][12][13] In 1999, she completed the first female free solo of the Brandler-Hasse Route (ED-: 5.10c A0), on the north face direct of the Cima Grande di Lavaredo; her last major alpine climb.

[15] In 1993, she went on an expedition to the west face of Makalu with Jeff Lowe and French mountaineering guide, Erik Decamp (who would later become her husband).

Lowe tried an alternative solo route while Destivelle and Decamp tried the West Pillar, however, both groups were unsuccessful due to severe snowfall.

[18] In January 1996, after the pair successfully completed a new route on the south face of Peak 4111 in Antarctica, Destivelle fell 20-metres through a cornice while momentarily unroped on the summit, and suffered a severe compound leg fracture.

[20][21] On a 1992 tour to the US, she free soloed the second half of El Matador 5.10d (6b+) on the Devils Tower in Wyoming, and Supercrack 5.10b (6a+), in Indian Creek, Utah (both are captured in the 1992 climbing film, Ballade à Devil's Tower), and in 1997, while four months pregnant, free soloed the Old Man of Hoy in Scotland (captured in the 1998 film, Rock Queen).

[6] When she became the first female recipient of the Piolet d'Or Lifetime Achievement Award in 2020, PlanetMountain said: "the 59-year-old Frenchwoman is considered one of the greatest climbers and mountaineers of all times".

[4][24] After the birth of Victor, Destivelle began to cut back on free solo and extreme climbs in the late 1990s and developed a career as a lecturer, speaker and a mountaineering writer.

[24] In 2011, in partnership with Bruno Dupety, she became a publisher at her firm, "Les Editions du Mont Blanc", a company specializing in books about mountaineering and alpinism.