The volatile organic carbon (VOC) and odours emitted during the aerobic biological processing of municipal solid waste (MSW) was studied in a pilot-scale reactor. VOCs were detected by different techniques on solid waste samples and the outlet air stream, before and after a biofilter. Organic compounds (alpha-pinene, beta-myrcene, D-limonene) were also measured in condensate water and leachate from the process. Results showed uniformity in the composition of the air in the solid waste samples, air sampled during the process and condensed water, indicating a matrix-derived origin of these compounds. Leachates, however, contained substances with a quite different molecular structure from the compounds identified in the gaseous fraction. Most of the substances in the gaseous effluent had a hydrocarbon-like structure, mainly terpenoids. The odour produced and detected through olfactometry agreed with GC-MS analyses. This was true above all for terpenes.