An electrical connector is an important component for achieving the interconnection of electric equipment. However, the degradation of contacting parts within the electrical connector under repetitive mechanical insertion and extraction operations causes a decrease in the contact reliability level, resulting in considerable safety hazards. The coating quality, determining the degree of degradation of contact pairs, is considered a critical factor in fabricating more reliable and safer electrical connectors. In this paper, a gold and nickel coating is deposited onto the surface of a pin within an electrical connector using magnetron sputtering and is compared to an electroplated pin, and the effects of different processing techniques on the microstructure, mechanical properties, and wear behavior are systematically investigated. The measurement results indicate that the surface quality (uniformity and defect density) and mechanical properties (hardness and elastic modulus) of the gold/nickel coating based on magnetron sputtering are significantly better than those achieved using electroplating, showing excellent wear properties and electrical contact stability after repetitive insertion–extraction operations. This study is critical for the development of advanced coatings using a novel deposition technique.