The skutterudite/electrode thermoelectric joints were fabricated with the insertion of Ti foil by spark plasma sintering. The interfacial microstructure and reliability of joints were studied during thermal duration test. A multilayer structure, which was composed of intermetallic compounds, was observed at the CoSb3/Ti interface after thermal aging of 20 days. The interfacial reactions and diffusion path between CoSb3 and Ti were discussed. The contact resistance of CoSb3/electrode junction was measured through four-probe method and the thermal contact resistance was calculated based on multilayer mode measurement. Effects of the contact resistivity on the performance of CoSb3-based device were discussed.