A new instrumental approach for collection of retention index data in the first (D-1) and second (D-2) dimensions of a comprehensive two-dimensional (2D) gas chromatography (GC x GC) experiment has been developed. First-dimension indexes were determined under conventional linear programmed temperature conditions (Van den Dool indexes). To remove the effect that the short secondary column imposes on derived D-1 indexes, as well as to avoid handling of pulsed GC x GC peaks, the proposed approach uses a flow splitter to divert part of the primary column flow to a supplementary detector to simultaneously generate a conventional D-1 chromatogram, along with the GCxGC chromatogram. The critical D-2 indexes (Kovats indexes) are based upon isovolatility curves of normal alkanes. in D-2 space, providing a reference scale against which to correlate each individual target peak throughout the entire GCxGC run. This requires the alkanes to bracket the analytes in order to allow retention interpolation. Exponential curves produced in the D-2 separation space require a novel approach for delivery of alkane standards into the D-2 column by using careful solvent-free solid-phase microextraction (SPME) sampling. Sequential introduction of alkane mixtures during GC x GC runs was performed by thermal desorption in a second injector which was directly coupled through a short transfer line to the entrance of the secondary column, just prior to the modulator so that they do not have to travel through the D-1 column. Thus, each alkane mixture injection was quantitatively focused by the cryogenic trap, then launched at predetermined times onto the D-2 column. The system permitted construction of an alkane retention map upon which bidimensional. indexes of a 25-perfume ingredient mixture could be derived. Comparison of results with indexes determined in temperature-variable one-dimensional (1D) GC showed good correlation. Plotting of the separation power in the second dimension was possible by mapping Trennzahl values throughout the D-2 space. The methodology was applied to the separation of a standard mixture composed of 25 analytes (very diverse in polarity and structure) suspected to be allergens in perfume samples. The method will allow straightforward determination of temperature-variable retention indexes of target analytes.