ABSTRACT: The detection of DNA is inhibited in cases of sexual assault involving condom use. Trace evidence, including condom lubricant residues, provides crucial associative evidence in such cases. The existing Fourier transform infrared spectroscopy (FTIR) methods for lubricant analysis and detection are limited with regard to sensitivity and discrimination. The aim of this research was to establish a new method as an alternative to FTIR for the analysis of condom lubricant residues. Pyrolysis gas chromatography-mass spectrometry (PyGC-MS) and GC-MS are highly sensitive methods of analysis for a wide range of chemical substances. PyGC-MS and GC-MS were used to analyze condom lubricants in standard solution, from clean swabs and from postcoital swabs. Pyrolysis of polydimethylsiloxane (PDMS) lubricant forms cyclic products known as cyclic dimethyl siloxanes (DMS), which are separated and detected by the GC-MS. The polyethylene glycol (PEG) lubricant can be analyzed by GC-MS directly from solution. The methods of extraction and analysis presented in this paper were shown to be significantly more sensitive than FTIR for the analysis of PDMS and PEG condom lubricants. PDMS was detected as low as 1 μg in standard solution and from clean swabs using the PyGC-MS method. PEG was detected as low as 0.5 μg from standard solution and 50 μg from clean swabs using the GC-MS method. Unfortunately, we were unable to provide further discrimination between condom brands and subbrands. The methods established throughout the research were used successfully to detect condom lubricants from donated postcoital swabs. Lubricants were detected in abundance on swabs 12 h postcoitus. Recommendations are made regarding implementation of new methods for routine analysis of casework samples along with strict pyrolysis interpretation criteria to minimize the possibility of misinterpretation of false positives.