Effective separation of electron-hole and utilization of hot charge carriers are known to be the most important factors influencing the activity of a good photocatalyst. Herein, we developed a 1D/2D heterojunction in the composite of CdS nanorod and g-C3N4 (CN) nanosheets. These two form a quasi-type-II junction at the heterointerface. The photoexcited electrons are supposed to be transferred from CN to CdS, as observed from the enhanced photoluminescence of CdS. Transient studies revealed an absolute dominance of CdS exciton formation even in the composite system, although the dynamics were substantially modified in the presence of CN. The rise time of CdS band edge excitons were increased in the composite material, owing to the migration of hot electrons from CN to CdS. The hot electron transfer time was found to be ∼0.5 ps (rate constant ∼1.98 ps-1). The excitons decay in a much slower manner than that of the pristine CdS, confirming enhanced electron population in CdS. This migration of charge carriers was found to be immensely dependent on the applied excitation photon energy. Efficient migration of charge carriers leads to enhanced photocatalytic activity in the composite and an increased evolution of H2 evolution rate was witnessed. This detailed spectroscopic study toward the mechanistic pathway of the catalytic activity of an 1D/2D heterocomposite would be immensely helpful in fabricating many other effective heterojunctions which will advance the catalysis research.