Abstract2D semiconductor heterostructures exhibit broad application prospects. However, regular nanochannels of heterostructures rarely caught the researcher's attention. Herein, a metal–organic framework (i.e., Cu3(HHTP)2) and transition metal dichalcogenides (i.e., MoS2)‐based multilayer van der Waals heterostructure (i.e., Cu3(HHTP)2/MoS2) realized band alignment‐dominated light‐driven ion transport and further light‐enhanced ionic energy generation. High‐density channels of the heterostructure provide high‐speed pathways for ion transmembrane transport. Upon light illumination, a net ionic flow occurs at a symmetric concentration, suggesting a directional cationic transport from Cu3(HHTP)2 to MoS2. This is because Cu3(HHTP)2/MoS2 heterostructures containing type‐II band alignment can generate photovoltaic motive force through light‐induced efficient charge separation to drive ion transport. After introducing into the ionic power generation system, the maximum power density under illumination can achieve notable improvement under different concentration differences. In addition to the photovoltaic motive force, type‐II band alignment and material defect capture‐induced surface charge increase also raise ion selectivity and flux, greatly facilitating ionic energy generation. This work demonstrates that 2D semiconductor heterostructures with rational band alignment can not only be a potential platform for optimizing light‐enhanced ionic energy harvesting but also provide a new thought for biomimetic iontronic devices.