The invention relates to a Pd quantum dot-modified TiO2 nanorod-based photoelectric chemical analysis method and application thereof. By means of making a relational diagram of the concentration of a standard PCB 101 solution and current, the concentration of PCB 101 in a to-be-measured solution can be obtained. Compared with the prior art, by constructing a Pd quantum dot-modified TiO2 nanorod with efficient photoelectric catalytic reduction activity, the method realizes efficient reduction for the PCB 101, obtains sensitive cathode photocurrent and realizes photoelectric chemical detection for the PCB 101; furthermore, due to the introduction of molecularly imprinted loci and the establishment of a reaction type analysis method, the selectivity of the analysis method is further improved, and the interference of coexisting easily oxidized pollutants in environmental water with PCB 101 detection is greatly reduced. The method is simple and easy to implement and high in sensitivity, has a limit of detection reaching up to 10-13mol/ L, is stable in electrodes and has good reproducibility.