We aimed to investigate how sulfur (S) application prior to oilseed rape cultivation influences the uptake of cadmium (Cd) by rice grown in low- and high-Cd soils. A pot experiment involving four S levels (0, 30, 60, 120 mg S kg⁻¹) combined with two Cd rates (low and high—0.35 and 10.35 mg Cd kg⁻¹, respectively) was conducted. Soil pore water during rice growth and plant tissues at maturity were analyzed. The soil pore water results indicated that S application decreased Cd solubility under submergence due to the S-induced increase of soil pH and the enhancement of sulfide formation in soil micropores. When S was applied at rates of 30, 60 and 120 mg S kg⁻¹, brown rice Cd concentrations decreased by 18%, 18%, and 55% (p < 0.05) in the low-Cd soil but increased by 20%, 40%, and 40% in the high-Cd soil compared with those in the non-S treatment. The different effects of S on Cd accumulation in brown rice were related to Cd-induced oxidative stress in the rice plants. In low-Cd soils, a S-induced increase in phytochelatins in rice roots restricted and inhibited Cd translocation in brown rice. In high-Cd soils, the Cd-induced oxidative stress in rice plants weakened the protective effects of S, while highlighted the promotion of Cd uptake by S. Overall, S fertilizer is recommended for oilseed rape–rice rotations in low-Cd paddy fields. In high Cd-contaminated fields, oilseed rape–rice rotations are suitable for the simultaneous remediation by oilseed rape and production of rice without S fertilization.