The volatile fraction of commercial cocoa powders was isolated using thin-layer high-vacuum distillation (TLHVD) of Soxhlet extracts. Calculated and experimental recovery of the internal standard n-undecanoic acid methylester did agree, and a good reproducibility was found for the procedure. Around 70 volatile compounds were identified and semi-quantified using internal standard-based gas chromatography (GC), coupled GC–mass spectrometry (GC–MS) and GC-olfactometry (GC-O). Dehydromevalonic acid lactone, (R)-(−)-pantolactone and two diastereomer solerols were identified for the first time after purification by micropreparative GC and re-analysis using GC–MS and chiral GC. Strong sensory contributions also came from acetic acid, 2/3-methyl butanoic acid, phenylacetaldehyde, furaneol, dihydroxymaltol, vanillin and phenylacetic acid.