Comprehensive GC in the reversed polarity mode i.e. a polar main column and an apolar secondary column have been used to differentiate cyclic olefins, dienes and cyclic dienes in high temperature Fischer-Tropsch (FT)-based fuels. The elucidation of the blobs in the contour plot was based on spectral data obtained by TOF-MS. The effectiveness of selective catalytic hydrogenation in transforming dienes into olefins could be studied. Dienes are prone to polymerisation by Diels-Alder reactions and dimers and trimers were detected in the 2-D plot by operating the MS in the ion extraction mode. Polymerisation is thought to be partially responsible for gum formation in high temperature FT-derived products.