Herein, the growth of pristine ZnO nanostructures thin film on p‐Si(100) by modified successive ionic layer adsorption‐reduction method, revealing significant improvement in the charge collection for ultraviolet light detection, is reported. The deposited ZnO exhibits spindle‐like and hexagonal structure that grows preferentially along the c‐axis. Two‐probe electrical measurements validate the rectifying nature of the constructed n‐ZnO/p‐Si(100), revealing a substantial 11.3‐fold increase in photocurrent at room temperature under 375 nm irradiation at +3 V working voltage. The drastic increase in photocurrent is linked to efficient charge separation caused by charge transfer and band bending effects, as indicated by microsecond time‐resolved absorption measurements, providing useful information for device development.