Fast and selective detectors are very interesting for comprehensive two-dimensional gas chromatography (GC×GC). This is particularly true if the detector system can provide additional spectroscopic information on the compound structure and/or functionality. Other than mass spectrometry (MS), only optical spectroscopic detectors are able to provide selective spectral information. However, until present the application of optical spectroscopy technologies as universal detectors for GC×GC has been restricted mainly due to physical limitations such as insufficient acquisition speed or high detection limits. A recently developed simultaneous-detection spectrometer working in the vacuum ultraviolet (VUV) region of 125 to 240 nm overcomes these limitations and meets all the criteria of a universal detector for GC×GC. Peak shape and chromatographic resolution is preserved and unique spectral information, complementary to mass spectrometry data, is gained. The power of this detector is quickly recognized as it has the ability to discriminate between isomeric compounds or difficult to separate structurally related isobaric species, thus, it provides additional selectivity. A further promising feature of this detector is the data analysis concept of spectral filtering, which is accomplished by targeting special electronic transitions that allows for a fast screening of GC×GC chromatograms for designated compound classes.