With vacuum thermal evaporation, the CuI film was deposited on quartz and n-GaN substrates, and the morphology, crystalline structure and optical properties of the CuI films were investigated. According to the XRD results, the CuI film preferentially grew along [111] crystal orientation on the GaN epilayer. With Au and Ni/Au ohmic contact electrodes fabricated on CuI and n-GaN, a prototype p-CuI/n-GaN heterojunction UV photodetector strong UV spectral selectivity was created. At 0 V and 360 nm front illumination (0.32 mW/cm2), the heterojunction photodetector displayed outstanding self-powered detection performance with the responsivity (R), specific detectivity (D*), and on/off ratio up to 75.5 mA/W, 1.27×1012 Jones, and ∼2320, respectively. Meanwhile, the p-CuI/n-GaN heterojunction photodetector had excellent atmosphere stability.