Hierarchical heterostructure photocatalysts with broad spectrum solar light utilization, particularly in the nearinfrared (NIR) region, are emerging classes of advanced photocatalytic materials for solar-driven CO 2 conversion into value-added chemical feedstocks. Herein, a novel two-demensional/three-demensional (2D/3D) hierarchical composite is hydrothermally synthesized by assembling vertically-aligned ZnIn 2 S 4 (ZIS) nanowall arrays on nitrogen-doped graphene foams (NGF). The prepared ZIS/NGF composite shows enhancement in photothermal conversion ability and selective CO 2 capture as well as solar-driven CO 2 photoreduction. At 273 K and 1 atm, the ZIS/NGF composite with 1.0 wt% NGF achieves a comparably high CO 2-toN 2 selectivity of 30.1, with an isosteric heat of CO 2 adsorption of 48.2 kJ mol −1. And in the absence of cocatalysts and sacrificial agents, the ZIS/NGF composite with cyclability converts CO 2 into CH 4 , CO and CH 3 OH under simulated solar light illumination, with the respective evolution rates about 9.1, 3.5, and 5.9 times higher than that of the pristine ZIS. In-depth analysis using in-situ irradiated X-ray photoelectron spectroscopy (ISI-XPS) in conjunction with Kelvin probe measurements reveals the underlying charge transfer pathway and process from ZIS to NGF.