We present a detailed study of post-deposition annealing effects on contact resistance of Au, Ti, Hf and Ni electrodes on Mg2Si thin films. Thin-film Mg2Si and metal contacts were deposited using magnetron sputtering. Various post-annealing temperatures were studied to determine the thermal stability of each contact metal. The specific contact resistivity (SCR) was determined using the Cross Bridge Kelvin Resistor (CBKR) method. Ni contacts exhibits the best thermal stability, maintaining stability up to 400 °C, with a SCR of approximately 10−2 Ω-cm2 after annealing. The increased SCR after high temperature annealing is correlated with the formation of a Mg-Si-Ni mixture identified by cross-sectional scanning transmission electron microscopy (STEM) characterization, X-ray diffraction characterization (XRD) and other elemental analyses. The formation of this Mg-Si-Ni mixture is attributed to Ni diffusion and its reaction with the Mg2Si film.