Two-dimensional (2D) atomic-layered semiconductors are important for next-generation electronics and optoelectronics. Here, we designed the growth of an MoSe2 atomic layer on a lattice-matched GaN semiconductor substrate. The results demonstrated that the MoSe2 films were less than three atomic layers thick and were single crystalline of MoSe2 over the entire GaN substrate. The ultrathin MoSe2/GaN heterojunction diode demonstrated ∼850 nm light emission and could also be used in photovoltaic applications.