To achieve high separation power of complex samples using multidimensional gas chromatography (MDGC), the selectivity of the employed stationary phases is crucial. The non-polar × polar column combination remains the most popular column set used in MDGC. However, resolution of mixtures containing light analytes possessing very similar properties remains a formidable challenge. The development of stationary phases that offer unique separation mechanisms have the potential to significantly improve MDGC separations, particularly in resolving co-eluted peaks in complex samples. For the first time, a stationary phase containing silver(I) ions was successfully designed and employed as a second dimension column using comprehensive two dimensional gas chromatography (GC × GC) for the separation of mixtures containing alkynes, dienes, terpenes, esters, aldehydes, and ketones. Compared to a widely used non-polar and polar column set, the silver-based column exhibited superior performance by providing better chromatographic resolution of co-eluted compounds. A mixture of unsaturated fatty acids was successfully separated using a GC × GC method in which the elution order in the second dimension was highly dependent on the number of double bonds within the sample.