The effect of interstitial Cu on the thermoelectric properties of TiNiSn was evaluated by microwave and spark plasma sintering. It is demonstrated that the interstitial Cu optimize the carrier concentration and mobility, and that segregation of Cu at grain boundaries makes an additional contribution to the electrical conductivity. The goal of great increasing the electrical conductivity while maintaining a high Seebeck coefficient is realized, resulting in a maximum of 3703.6 μWm−1K−2 at 673 K. Furthermore, the samples enhance the high-frequency phonon scattering by introducing more point defects. And the mass fluctuation scattering and stress field fluctuation scattering induced by the interstitial Cu further decrease the lattice thermal conductivity to 1.91 Wm−1K−1 at 773 K, a reduction of 64.7 % compared to the pure sample. The dimensionless figure of merit (ZT) of the TiNiCu0.055Sn is even higher by 78.7 %, with a maximum of 0.62.