Just as the heterojunctions in physics, donor–acceptor (D‐A) heterostructures are an emerging class of photoactive materials fabricated from two semiconductive components at the molecular level. Among them, D‐A hybrid heterostructures from organic and inorganic semiconductive components have attracted extensive attention in the past decades due to their combined advantages of high stability for the inorganic semiconductors and modifiability for the organic semiconductors, which are particularly beneficial to efficiently achieve photoinduced charge separation and transfer upon irradiations. In this review, by analogy with the heterojunctions in physics, a definition of the D‐A heterostructures and their general design and synthetic strategies are given. Meanwhile, the D‐A hybrid heterostructures are focused on and their recent advances in potential applications of photochromism, photomodulated luminescence, and photocatalysis summarized.