This research investigated the effects of Cu content on the interfacial IMCs in low-Ag Sn–0.7Ag–xCu–3.5Bi–0.05Ni (x = 0.3, 0.5, 0.7, and 1.5 wt%, respectively) solder joints by deep-etching method and SEM observation. Experimental results indicated that as Cu content increased in the solder, the grain size of the IMCs increased and the thickness of the IMCs decreased on Cu substrate. When the concentration of Cu in the solder was 0.3 wt%, the IMC on the soldering interface was (Cu, Ni)6Sn5. The concentration of Ni in (Cu, Ni)6Sn5 IMC was significantly suppressed by the increase of Cu content in the solder. As Cu content increased to 1.5 wt%, the concentration of Ni in the IMC decreased to 0 and the IMC transformed from (Cu, Ni)6Sn5 to Cu6Sn5. Due to the increase of Cu content, more and more (Cu, Ni)6Sn5 grains nucleated on Ni substrate, and the morphology of (Cu, Ni)6Sn5 transformed from polyhedrons to tiny prisms.