•The application, potential, and limitations of GC × GC in forensic science were reviewed.•Only a limited number of publications were found using GC × GC for forensic investigations.•GC × GC data treatment and analysis for forensic comparison were described in detail.•Application of chemometric methods on GC × GC data for forensic comparison was reviewed. In this study, the application of comprehensive two-dimensional (2D) gas chromatography (GC × GC) in forensic science is reviewed. The peer-reviewed publications on the forensic use of GC × GC and 2D gas chromatography with mass spectrometric detection (GC × GC–MS) have been studied in detail, not only to provide an overview, but also to analyze and understand the potential and limitations of this relatively novel analytical technique in forensic investigations. In order to make comprehensive GC × GC a powerful tool in forensic laboratories involved in chemical analysis, further developments are needed with respect to data analysis. Easy-to-use and “fit-for-forensic purpose” data analysis and chemometric tools will allow forensic analytical chemists to explore and compare the comprehensive data to provide solutions for relevant questions in criminal investigations.