Dissimilar materials of copper (Cu) to aluminum (Al) with nickel-phosphorus (Ni-P) coatings were joined using resistance spot welding. The Ni-P coatings were electroless plated on the Al surfaces to eliminate the formation of brittle Cu-Al intermetallic compounds (IMCs) at the faying interface of Cu to Al. Three welding schedules with various heat input were used to produce different interfacial microstructure. The evolution of interfaces in terms of phase constitution, elemental distribution, and defects (gaps and voids) was characterized and the formation mechanisms were elucidated. During the welding, the bonding between Cu and Ni-P form through solid-state diffusion, while the faster diffusion rate of Cu relative to Ni and P atoms promotes the generation of sub-micro voids. As the heat input increases, gaps at the Cu/Ni-P interface diminish accompanied by increase of sub-micro voids. A moderate schedule helps to remove the gaps and inhibit the voids formation. An Al3Ni layer and nanovoids were found around the interface of Ni-P/Al. The increased heat input decreases the grain size of Al3Ni at the interface by eutectic remelting and increases the nanovoids by enhanced nanoscale Kirkendall effect.