The durability of Ni electrodes, which are often used for Mg2Si thermoelectric chips, is poor at high working temperatures because of deposition of Mg at the Mg2Si/Ni interface and on the surface. Hence, a "Mg2Si/barrier material/Ni'' structure was adopted instead of direct adhesion of Ni to Mg2Si. Ti, TiSi2, and TiN were selected as candidate materials for the barrier layer between Mg2Si and Ni, and the barrier effect, adhesion, and contact resistance of each of these materials were evaluated. After the samples had been annealed at 873 K for 1 h, Mg appeared on the Ti surface and TiSi2 deposited on Mg2Si; however, no Mg was detected on the surface of TiN or in the inner part of the Ni electrode. Continuous, low contact resistance was also observed for Mg2Si/TiN/Ni samples. TiN does not adhere strongly to Mg2Si but is a promising barrier material for Mg2Si/Ni interfaces.