Variations in the amounts of volatile alcohols and esters from subcutaneous fat have been assessed during the dry-curing process (1022 days) of Iberian ham according to a purge and trap-gas chromatography-mass spectroscopy method, using the same hams throughout the process. During processing time, the subcutaneous adipose tissues of ten hams obtained from five Iberian pigs fed on acorns and pasture were sampled and analyzed once per month. Fifteen alcohols and five esters have been identified. All volatile alcohols detected in this work have been previously identified by other authors on Iberian ham, except 3-buten-2-ol, 5-methyl-3-hexanol and 2-isononanol. A linear discriminant analysis (LDA) was applied and the two discriminant functions were obtained using backward stepwise analysis retaining the following variables: butyl ester formic acid, 1-penten-3-ol, methyl ester 2-propenoic acid, 5-methyl-3-hexanol, 1-nonanol, ethyl ester pentanoic acid, ethyl ester hexanoic acid, 2-isononanol, ethanol and 3-buten-2-ol. A complete separation among the three periods was obtained, suggesting that the retained variables are powerful descriptors to distinguish samples from these three dry-curing stages.