In this article, we report the growth of zinc‐tin nitride (ZnSnN2) thin films as a potential absorber for photovoltaic applications by fabricating a heterojunction of n‐ZnSnN2/p‐SnO. The performance of the heterojunction has been monitored through selective deposition of top electrode with different materials (Ni/Au or Al). The electron‐transfer process from the ZnSnN2 layer to the cathode is facilitated by selecting metal electrode with relatively low work function, which also boosts up the electron injection or/and extraction. The diode exhibits a good J–V response in the dark with a rectification ratio of 3 × 103 at 1.0 V and an ideality factor of 4.2 in particular with Al as the top electrode. Under illumination, the heterostructure solar cell demonstrates a power conversion efficiency of ≈0.37% with an open circuit voltage of 0.25 V and a short circuit current density of 4.16 mA cm−2. The prime strategies, on how to improve solar cell efficiency concerning band offsets and band alignment engineering are also discussed.