Volatile and semi-volatile organic compounds are some of the most widely studied samples. Traditional analytical methods rely on single dimension (single column) gas chromatography (GC) coupled to universal detectors (such as flame ionization, thermal conductivity or electron capture) and/or mass selective detectors such as mass spectrometry (MS). More recently, the use of comprehensive two-dimensional gas chromatography (GC×GC), a dual column separation system, has gained significant popularity for complex sample analysis. Targeted species in heavy matrix, screening of difficult samples, and both identification and quantification of compounds below traditionally reported levels of detection (L.O.D.’s) are some of the advantages of using GC×GC. The ability to screen complex samples and the simultaneous quantitative detection of compounds found at sub part-per-billion (ppb) levels is a very powerful attribute when targeting biosignatures in the search for life. Recent advances to GC×GC instrumentation have made this technique more robust and applicable to future planetary science instrumentation in which organic compound characterization is of mission importance. This paper introduces GC×GC and explore the opportunities that make it a viable analytical tool for the advanced analysis of environmental samples (air, soil and liquid) and its applicability to future habitable world space missions.