The prodigious employment of fossil fuels to conquer the global energy demand is becoming a dreadful threat to the human society. This predicament is appealing for a potent photocatalyst that can generate alternate energy sources via solar to chemical energy conversion. With this interest, we have fabricated a ternary heterostructure of Ti3C2 nanosheet modified g‐C3N4/Bi2O3 (MCNRBO) Z‐scheme photocatalyst through self‐assembly process. The morphological analysis clearly evidenced the close interfacial interaction between g‐C3N4 nanorod, Bi2O3 and Ti3C2 nanosheets. The oxygen vacancy created on Bi2O3 surface, as suggested by XPS and EPR analysis, supported the Z‐scheme heterojunction formation between g‐C3N4 nanorod and Bi2O3 nanosheets. The collaborative effect of Z‐scheme and Schottky junction significantly reduced charge transfer resistance promoting separation efficiency of excitons as indicated from PL and EIS analysis. The potential of MCNRBO towards photocatalytic application was investigated by H2O2 and H2 evolution reaction. A superior photocatalytic H2O2 and H2 production rate for MCNRBO is observed, which are respectively around 5 and 18 folds higher as compared to pristine CNR nanorod. The present work encourages for the development of a noble, eco‐benign and immensely efficient dual heterojunction based photocatalyst, which can acts as saviour of human society from energy crisis.