Magnesium silicide-based materials are a very promising class of thermoelectric materials with excellent potential for thermoelectric waste heat recovery. For the successful application of magnesium silicide-based thermoelectric generators, the development of long-term stable contacts with low contact resistance is as important as material optimization. We have therefore studied the suitability of Ni as a contact material for magnesium silicide. Co-sintering of magnesium silicide and Ni leads to the formation of a stable reaction layer with low electrical resistance. In this paper we show that the contacts retain their low electrical contact resistance after annealing at temperatures up to 823 K for up to 168 h. By employing scanning electron microscope analysis and time-of-flight (ToF)–secondary ion mass spectrometry, we can further show that elemental diffusion is occurring to a very limited extent. This indicates long-term stability under practical operation conditions for magnesium silicide/nickel contacts.