Two-dimensional materials garner increasing interest in next-generation electronics and optoelectronic devices due to their atomic-thin nature and distinctive physical properties. Building on these advances, we present the successful synthesis of a heterostructure composed of the semi-metallic Ti3C2-MXene and the semiconducting WSe2, in which the atomic layers are vertically aligned. The wet impregnation method effectively synthesizes an atomically thin Ti3C2-MXene/WSe2 heterostructure characterized by AFM, Raman and TRPL analysis. In addition, the current-voltage characteristics at the heterostructure reveal the Schottky junction probed by the scanning tunneling microscopy and the conductive atomic force microscopy tip. The Schottky heterojunction also exhibits enhanced photocatalytic properties by improving the photogenerated charge carriers and inhibiting recombination. This work demonstrates the unique 2D-2D Ti3C2-MXene/WSe2 vertical heterojunction possesses superior photon trapping ability and can efficiently transport photogenerated charge carriers to the reaction sites to enhance photocatalysis performance.