Pelmo was the first peak in the Dolomites to be climbed, on 19 September 1857, by the Irishman John Ball, via the Ball ledge. Leaving from Borca di Cadore, he was accompanied by a local guide, presumably named Giovanni Battista Giacin, but the latter did not reach the summit. Ball chose the Pelmo for his first ascent because he found it the most beautiful of all the Dolomite mountains he had seen, and easier than the majestic Antelao.

Three alpine refuges stand at the foot of the Pelmo: the Venezia-Alba Maria De Luca refuge, the Città di Fiume refuge and the Passo Staulanza refuge. The most famous mountaineering routes on Pelmo are the classic Simon-Rossi along the wall and the north edge, which, however, became dangerous after the 2011 landslides. There are a few variants along the route. Another important route is the Pilastro Fiume, which climbs the imposing north-eastern edge until it joins the Simon-Rossi route.

The counter-clockwise tour of the Pelmo starts from the Staulanza Hut (1773 m) following path no. 472 in the direction of the Venezia Hut (1946 m). The time required to reach this first destination is about 2½ hours. From the Venezia refuge, continue towards the Val d’Arcia pass (2476 m) along trail no. 480. From here, the route descends along the northern scree slopes of Pelmo until it rejoins path no. 472, which leads back to Passo Staulanza. The total time expected for this tour is approximately 6 hours.