An analytical method was developed for C8–C11 aliphatic aldehydes in wine consisting of solid phase extraction (SPE) followed by multidimensional gas chromatography/mass spectrometry (MDGC/MS). The method achieves low detection limits (<30 ng L−1), minimises problems of blank contamination and shows high repeatability (RSD% < 5%), but strong matrix effects were noticed during validation. These matrix effects were attributed to strong interactions between aliphatic aldehydes and other matrix elements. Three fractions were differentiated: free extractable aldehydes, aldehydes bound in hydrophilic complexes (extractable in the presence of acetaldehyde) and aldehydes bound in hydrophobic complexes (extractable in the presence of heptanal). The distribution of the three aldehyde species in wine samples was estimated using a surrogate (3,5,5-trimethylhexanal) and an internal standard (methyl phenylacetate) in double determinations (directly and after incubation with 1000 mg L−1 acetaldehyde). These components had a clear additive sensory effect in mixtures and odour thresholds in wine were very low. This caused that although they were present at very low levels, in 2 out of 24 white wine samples were clearly above threshold, and in six more were at levels close to threshold. These results suggest that these components are active contributors to the citrus fruit notes of some white wines. (We recommend that you consult the full text of this article).