•Prescribed fire caused considerable C losses at the 0–1 cm depth, mostly from POM.•Uneven combustion resulted in few qualitative changes in the remaining organic matter.•Bioavailable N showed transient increases, while S and P gradually declined after fire.•Steadier nutrient inputs were derived from the breakdown of particulate charcoal. High-mountain soils are rich in partially decomposed organic matter, which is highly sensitive to mineralization and fire. Prescribed burning is performed in the Pyrenees to keep subalpine grasslands open for grazing. The compositions of the ash, litter and duff layers, and the particulate organic matter (POM) of the topsoil in the 0–1, 1–2, 2–3, and 3–5 cm depths were analyzed in relation to the nutrient availability after the prescribed burning of a stand encroached by erizón (Echinospartum horridum). The concentrations of C, N, P, and S and organic components (nonstructural, hemicellulose, cellulose, and lignin-type) were determined before the prescribed burn and 0, 6, 12, 18, and 24 months after the prescribed burn. The fire consumed the aboveground biomass, the litter and part of the duff layer, and the most thermostable (i.e., lignin-type) components and the least volatile elements (P, S) were selectively preserved in the resulting ash. Prescribed burning caused significant losses of organic-C and N only in the 0–1 cm depth (–72% and –68%, respectively). The organic-C loss was mostly (82%) from the POM, whereas the N loss was from more similar proportions of the POM (57%) and the nonparticulate organic matter (NPOM) (43%). However, few changes were observed in the composition of the organic matter, which pointed to a largely uneven combustion that resulted in a substantial part of the organic matter remaining largely untouched by the fire. After 6 months, the duff layer was depleted in hemicellulose by 32% compared to immediately after the burn, and fragmentation of the POM into the NPOM was observed. During the second spring, N- and P-rich charred POM were incorporated into the top 1 cm, while C-rich charcoal particles underwent fragmentation and vertical transport into the deeper soil. The preburn ecosytem was limited by P, and likely also by S. The plant available N showed transient increases of 1.5–2.1 times the immediate postburn levels for nitrate-N at 12 months after burning, and of up to 10–20 times for ammonium-N at 18 months. In contrast, the concentrations of plant-available P and S gradually declined to 1.8–3.3 and 1.8–4.0 times, respectively, lower at 24 months after the burn. Results indicated that fire-induced increases in the nutrient availability can be short-lived in high-mountain habitats, but steadier and likely more persistent nutrient inputs can derive from the gradual breakdown of charred organic matter.