In situ construction of two-dimensional (2D)/2D pg-C3N4/Ti3AlC2 MAX heterojunction was achieved using a protonated assisted sonication approach, while TiO2 nanoparticles were embedded over the layered heterostructure using a sol-gel method. This multiheterojunction system exhibits proficient charge transfer and superior activity toward photocatalytic reduction of CO2 through dry reforming of methanol (DRM). Using pg-C3N4/Ti3AlC2/TiO2 composite, H-2 and CO production rates at 91.9 and 4.97 mmol (g of cat.)(-1) h(-1) were achieved, which are 18- and 6-fold higher than using pristine pg-C3N4, respectively. The enhancement in photocatalytic activity is mainly attributed to intimate interfacial contact due to the formation of a multiheterojunction for better light absorption, boosted electron separation, and stronger photoreductive potential. More importantly, CO2 reduction with H2O produces CO-rich syngas; however, the methanol/water mixture promoted hydrogen-rich syngas production. Higher quantum yield and prolonged stability are further achieved over the composite catalyst, attributed to the exfoliated 2D Ti3AlC2 MAX structure with strong metal/support interaction. This work demonstrates DRM as a potential approach to get hydrogen-rich syngas and provides a new pathway for the construction of highly stable 2D MAX based structured composite for water splitting and CO2 reforming applications.