Pluto is covered by numerous deposits of methane, either diluted in nitrogen or as methane-rich ice. Within the dark equatorial region of Cthulhu, bright frost containing methane is observed coating crater rims and walls as well as mountain tops, providing spectacular resemblance to terrestrial snow-capped mountain chains. However, the origin of these deposits remained enigmatic. Here we report that they are composed of methane-rich ice. We use high-resolution numerical simulations of Pluto's climate to show that the processes forming them are likely to be completely different to those forming high-altitude snowpack on Earth. The methane deposits may not result from adiabatic cooling in upwardly moving air like on our planet, but from a circulation-induced enrichment of gaseous methane a few kilometres above Pluto's plains that favours methane condensation at mountain summits. This process could have shaped other methane reservoirs on Pluto and help explain the appearance of the bladed terrain of Tartarus Dorsa.