This study investigates electromigration in Bi2Te3 thermoelectric (TE) material systems and the effectiveness of the diffusion barrier under current. The Peltier effect on the interfacial reaction was decoupled from the effect of electromigration. After connecting p- and n-type Bi2Te3 to Sn3Ag0.5Cu (SAC305) solders, different current densities were applied at varying temperatures. The Bi2Te3 samples were fabricated by the spark plasma sintering technique, and an electroless nickel-phosphorous (Ni-P) layer was deposited at the solder/TE interfaces. The experimental results confirm the importance of the Ni diffusion barrier in joint reliability. Intermetallic compound layers (Cu,Ni) 6Sn5 and NiTe formed at the solder/Ni-P and Ni-P/substrate interfaces, respectively. The experimental results indicate that the mechanism of NiTe and (Cu,Ni)6Sn5 compound growth was dominated by the Peltier effect at high current density. When the current density was low, the growth of NiTe was affected by electromigration but the changes of thickness for (Cu,Ni)6Sn5 were not obvious.