The determination of the presence and the composition of residues from organic materials on archeological objects allows the behavior of our prehistoric ancestors to be better understood. The functional analysis of tools used for daily life activities, such as hunting or hide working, represents an important source of information. However, the chemical characterization of residues from archeological artifacts represents an analytical challenge. On one hand, the residues are made of different natural materials containing hundreds of chemicals. This complexity requires advanced analytical procedures to separate and identify the constituents. On the other hand, the low quantity and the advanced degradation require sensitive and non-destructive methods. In this study, an approach employing headspace sampling (solid-phase microextraction) with comprehensive two-dimensional gas chromatography coupled to high-resolution-time-of-flight mass spectrometry was developed for the characterization of adhesive residues on simulated archeological artifacts. First, the performance of the analytical system was evaluated on a standard mixture and a pine resin sample. Next, adhesives and adhesives mixtures were analyzed that represented typical compositions that have been witnessed in archaeological applications. This analytical approach is a gateway into new potential for headspace organic residue characterization as a first step of analysis prior to altering residues for additional characterization.