During decomposition of mammalian remains, volatile organic compounds (VOCs) are released into the environment. Comprehensive two-dimensional gas chromatography (GC×GC) assists in analyzing these VOCs with its increased separation power and sensitivity. This study analyzes the temporal changes in decomposition VOCs from human analogs in a tropical climate. For this specific application, the use of a gas chromatograph coupled with a quadrupole mass spectrometer (qMS) and simultaneous flame ionization detector (FID) retrofitted with a reverse fill/flush (RFF) flow modulator is reported for the first time. The method was used to examine postmortem processes to monitor chemical changes from pig carcasses. Approximately 30 compounds were tentatively identified from the decomposing remains, representing consistent trends in the decomposition VOC profile at a new location. As interest increases worldwide in collecting VOC samples as evidence in forensic casework, this type of instrumentation could become a valuable tool in crime laboratories.