In order to identify the effect on the properties and behavior of tin-zinc-bismuth (Sn-8 wt% Zn-3 wt% Bi or Sn-13.6 at.% Zn-1.6 at.% Bi) based solders produced by adding nickel (Ni) nano-particles, the interfacial microstructure between plain and composite solders with newly developed immersion silver (Ag) plated copper (Cu) substrates has been investigated as a function of reaction time, at various temperatures. For plain Sn-8Zn-3Bi solder joints, a scallop-shaped Cu-Zn-Ag intermetallic compound layer was found to adhere to the surface of the immersion Ag-plated Cu substrate. However, after addition of Ni nano-particles into the Sn-8Zn-3Bi solder, Cu-Zn-Ag (at the bottom) and (Cu, Ni)-Zn (at the top) intermetallic compound layers were observed at the interfaces. In addition, these intermetallic compound layer thicknesses increased substantially with increases in the temperature and reaction time. In the solder ball region, needle-shaped α-Zn rich phase and spherically-shaped Bi-particles appeared to be homogeneously distributed throughout a beta-tin (β-Sn) matrix. However, after the addition of Ni nano-particles, needle-shaped α-Zn rich phase appeared that exhibited a fine microstructure, due to the heterogeneous nucleation of the Ni nano-particles. The calculated activation energy for the Cu-Zn-Ag intermetallic compound layer for the plain Sn-8Zn-3Bi solder/immersion Ag-plated Cu system was 29.95 kJ/mol - while the activation energy for the total [Cu-Zn-Ag + (Cu, Ni)-Zn] intermetallic compound layers formed in the Sn-8Zn-3Bi-0.5Ni (Sn-13.6 at.% Zn-1.6 at.% Bi ∼1 at.% Ni) composite solder/immersion Ag-plated Cu system was 27.95 kJ/mol. Addition of Ni nano-particles reduces the activation energy which enhanced the reaction rate as we know that lower the activation energy indicates faster the reaction rate. © 2014 Springer Science+Business Media New York.