In the study reported herein, silver-coated copper (Ag/Cu) powder was modified with alkanethiols featuring alkyl chains of different lengths, namely butyl, octyl, and dodecyl, to improve its thermal stability. The modification of the Ag/Cu powders with adsorbed alkanethiols was confirmed by scanning electron microscopy with energy dispersive spectroscopy, X-ray photoelectron spectroscopy, and thermogravimetric analysis. Each powder was combined with an epoxy resin to prepare an electrically conductive film. The results confirmed that the thermal stability of the films containing alkanethiol-modified Ag/Cu powders is superior to that of the film containing untreated Ag/Cu powder. The longer the alkyl group in the alkanethiol-modified Ag/Cu powder, the higher the initial resistance of the corresponding electrically conductive film and the lower the increase in resistance induced by heat treatment.