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The development of cost-effective co-catalysts of high photocatalytic activity and recyclability is still a challenge in the energy transformation domain. In this study, 0D/2D Schottky heterojunctions, consisting of 0D ZnO and 2D Ti₃C₂, were successfully synthesized by the electrostatic self-assembling of ZnO nanoparticles on Ti₃C₂ nanosheets. In constructing these heterojunctions, Ti₃C₂ nanosheets acted as a co-catalyst for enhancing the transfer of excitons and their separation to support the photocatalytic response of ZnO. The as-prepared ZnO/Ti₃C₂ composites demonstrate an abbreviated charge transit channel, a huge interfacial contact area and the interfacial electrons’ transport potential. The extended optical response and large reactive area of the ZnO/Ti₃C₂ composite promoted the formation of excitons and reactive sites on the photocatalyst’s surface. The ZnO/Ti₃C₂ Schottky heterojunction showed significantly high photocatalytic activity for hydrogen production from a water–ethanol solution under the light illumination in the visible region. The hydrogen evolution overoptimized the ZnO/Ti₃C₂ composition with 30 wt.% of Ti₃C₂, which was eight times higher than the pristine ZnO. These findings can be helpful in developing 0D/2D heterojunction systems for photocatalytic applications by utilizing Ti₃C₂ as a low-cost co-catalyst.