Gas chromatography-ion mobility spectrometry (GC-IMS) has recently gained increasing attention for the analysis of volatile compounds due to its high sensitivity, selectivity, and robust design. Peak shape distortion, including peak tailing or broadening, are well known challenges in chromatographic analysis that result in peak asymmetry and decreased resolution. However, in IMS analysis peak tailing, which is independent on the column separation technique, have also been observed. As high boiling substances, such as monoterpenes, are mainly affected by enlarged peak tailing in GC-IMS, we propose that condensation or adsorption effects within the “cold” IMS cell, which is commonly operated at 45 °C–90 °C, are the root cause. To avoid condensation and to decrease peak tailing, we used a prototypic high temperature ion mobility spectrometry (HTIMS) in this work, which allows an increase of the IMS drift tube temperature up to 180 °C. This HTIMS was coupled to a GC column separation and used to analyse the peak shape of homologues series of ketones, alcohols, aldehydes, as well as high boiling fragrance compounds, such as monoterpenes and phenylpropanoids. While we were able to show that an increased IMS drift tube temperatures correlates well with improved peak shapes, the GC parameters of the HS-GC-HTIMS method, however, were found to have little effect on the peak shapes in IMS spectra. In particular monoterpenes, which display intense peak tailing at lower IMS drift tube temperatures, show significant improvement of the peak shape at higher IMS drift tube temperatures. This leads to the assumption that high boiling substances indeed undergo condensation effects within the IMS cell at low drift tube temperatures. For many separation tasks, such as the separation of the phenylpropanoids eugenol and isoeugenol, comparably low IMS temperatures of 120 °C are already sufficient to achieve a resolution above 1.5. However, the optimal drift tube temperature is dependent on the substance class. While the aspect ratio increases steadily for most monoterpenes, phenylpropanoids and aldehyde monomer peaks investigated, an optimal aspect ratio was found for ketones between 140 °C and 160 °C and alcohols between 120 °C and 140 °C. Lastly, the change of the reduced mobility K0 with the increase of drift tube temperature was analysed. Compounds with similar chemical structure, such as the alcoholic monoterpenes citronellol and geraniol or the phenylpropanoids eugenol and isoeugenol show similar shifts of the K0 value. Substances which differ in their chemical structure, such as the aldehyde monoterpenes citral and cinnamal have substantially different shifts of the K0 value. With a future large substance database, the temperature dependant slope of the K0 value of a substance could be used to identify the substance groups of unknown molecules. Furthermore, substances with the same drift time but different chemical composition could be separable through a change in drift tube temperature.