A capillary column coated with nanostructured silver coating was fabricated for gas chromatography. The nanostructured silver coating, about 80-120 nm in thickness, was prepared as the stationary phase via silver mirror reaction, and was characterized by SEM and EDS. The column was evaluated using different types of model analytes, including n-alkanes, n-alcohols, benzenes, and Grob mixture. A baseline separation of ten n-alkanes on the silver column (15 m × 0.20 mm i.d.) was achieved within 3.5 min through the main hydrophobic mechanism. A mixture of six n-alcohols, or another mixture containing three butanol isomers and two octanol isomers, was separated well on the column. The column separated some benzenes containing benzene, toluene, ethylbenzene, p-xylene, o-xylene, styrene, benzaldehyde, and benzyl alcohol. A Grob mixture containing seven analytes was also separated successfully. Based on a multiple retention mechanism such as hydrophobic, dipole-dipole, and dipole-induced dipole interactions, the silver column achieved a good separation of twelve different types of compounds within 2.5 min. The column presented satisfactory separation repeatability with relative standard deviation of retention time between 0.073% and 0.591%. The results indicate that the silver column is promising for gas chromatographic separation.