This study investigated the beneficial effect of molybdenum (Mo) application on rape plants (Brassica napus L.) grown in a soil polluted by cadmium (Cd). A pot experiment was conducted to determine how different concentrations of exogenous Mo (0, 50, 100, and 200 mg/kg) affect plant physiology, biomass, photosynthesis, cation uptake, and Cd translocation and enrichment in rape plants under Cd stress (0.5 and 6.0 mg/kg). Under single Cd treatment, plant physiological and biochemical parameters, biomass parameters, leaf chlorophyll fluorescence parameters, and macroelement uptake of rape plants decreased, while their malonaldehyde content, proline content, non-photochemical quenching coefficient, and Cd uptake significantly increased, compared to those of the control group (p-values < 0.05). High-Cd treatment resulted in much larger changes in these parameters than low-Cd treatment. Following Mo application, the accumulation of malondialdehyde and proline decreased in the leaves of Cd-stressed plants; reversely, the contents of soluble protein, soluble sugar, and chlorophyll, and the activities of superoxide dismutase and glutathione peroxidase, all increased compared to those of single Cd treatment (p-values < 0.05). Exogenous Mo application promoted shoot and root growth of Cd-stressed plants in terms of their length, fresh weight, and dry weight. The negative effect of Cd stress on leaf chlorophyll fluorescence was substantially mitigated by applying Mo. Exogenous Mo also improved the uptake of inorganic cations, especially potassium (K+), in Cd-stressed plants. After Mo application, Cd uptake and accumulation were inhibited and Cd tolerance was enhanced, but Cd translocation was less affected in Cd-stressed plants. The mitigation effect of Mo on Cd stress in rape was achieved through the immobilization of soil Cd to reduce plant uptake, and improvement of plant physiological properties to enhance Cd tolerance. In conclusion, exogenous Mo can effectively reduce Cd toxicity to rape and the optimal Mo concentration was 100 mg/kg under the experimental conditions.