Combining qualitative data from the chromatographic structure of 2‐D gas chromatography with flame ionization detection (GC×GC‐FID) and that from gas chromatography‐mass spectrometry (GC/MS) should result in a more accurate assignment of the peak identities than the simple analysis by GC/MS, where coelution of analytes is unavoidable in highly complex samples (rendering spectra unsuitable for qualitative purposes) or for compounds in very low concentrations. Using data from GC×GC‐FID combined with GC/MS can reveal coelutions that were not detected by mass spectra deconvolution software. In addition, some compounds can be identified according to the structure of the GC×GC‐FID chromatogram. In this article, the volatile fractions of fresh and dehydrated pineapple pulp were evaluated. The extraction of the volatiles was performed by dynamic headspace extraction coupled to solid‐phase microextraction (DHS‐SPME), a technique appropriate for slurries or solid matrices. Extracted analytes were then analyzed by GC×GC‐FID and GC/MS. The results obtained using both techniques were combined to improve compound identifications.