In this paper, a superior-quality InN/p-GaN interface grown using pulsed metalorganic vapor-phase epitaxy (MOVPE) is demonstrated. The InN/p-GaN heterojunction interface based on high-quality InN (electron concentration 5.19 × 1018 cm−3 and mobility 980 cm2/(V s)) showed good rectifying behavior. The heterojunction depletion region width was estimated to be 22.8 nm and showed the ability for charge carrier extraction without external electrical field (unbiased). Under reverse bias, the external quantum efficiency (EQE) in the blue spectral region (300–550 nm) can be enhanced significantly and exceeds unity. Avalanche and carrier multiplication phenomena were used to interpret the exclusive photoelectric features of the InN/p-GaN heterojunction behavior.