The first two homoleptic Ni0 isocyanide complexes that exhibit photoluminescence from long-lived excited states are presented. Electrochemical studies indicate that in one of the complexes significant geometrical distortion occurs upon metal oxidation. The observation of luminescence, even though currently restricted to low temperatures, is an important proof-of-concept in the search for earth-abundant alternatives to photoactive complexes made from precious metals. The prospect of using Ni0 isocyanide complexes as luminophores, photoredox catalysts, or dyes in solar cells, is highly attractive.