Two-dimensional transition-metal dichalcogenides (TMDCs) are notable materials owing to their flexibility, transparency, and appropriate bandgaps. Because of their unique advantages, TMDC p-n diodes have been studied for next-generation electronics and optoelectronics. However, their efficiency must be increased for commercialization. In this study, we demonstrated a heterostructure composed of few-layer ReS2 and WSe2. This few-layer ReS2/WSe2 heterostructure exhibits a p-n junction and an n-n junction in different gate-bias regimes. In the p-n junction regime, the heterostructure shows outstanding rectification behavior. Additionally, we identify three carrier-transfer mechanisms - direct tunneling, Fowler-Nordheim tunneling, and the space charge region - depending on the drain bias. Furthermore, the photovoltaic effect is observed in this few-layer ReS2/WSe2 heterostructure. As a result, a high fill factor (≈ 0.56), power conversion (≈ 1.5%), and external quantum efficiency (≈ 15.3%) were obtained. This study provides new guidelines for flexible optoelectronic devices.