Rice consumption is a key Cd exposure pathway, which poses a health risk to humans. Reducing cadmium (Cd) concentrations in rice remains challenging. In this study, a pot experiment was conducted to examine the effects of foliar spray of Zn combined with organic matters (including Zn–lysine (Zn-Lys), Zn–fulvic acid (Zn-FA), Zn–amino acid (Zn-AA), and Zn combined with glutathione (Zn + GSH)) on Cd accumulation in rice grains. Compared with the control group, all treatment groups exhibited reduced Cd concentration in rice grains, while improving plant growth, and reducing Cd transport from other tissues to the grains. Zn–FA was found to be the most effective fertilizer, which considerably reduced Cd concentrations in grains from 0.77 ± 0.068 to 0.14 ± 0.021 mg/kg and yielded reductions of up to 81%, which is within the Chinese food maximum tolerable limit of 0.2 mg/kg. Furthermore, the analysis of the chemical forms of Cd of rice tissues indicated that the treatment groups had increased proportions of integrated with pectates and protein in the stems. Except for the group treated with Zn–Lys spray, the percentages of undissolved Cd phosphate in the leaves were increased in all treatment groups, which reduced Cd toxicity to rice plants. The foliar application of Zn combined with organic matters may be a promising strategy to decrease Cd concentration in rice grains cultivated in severely Cd-contaminated agricultural soil, particularly in the karst area in southwest China with limited available cultivable agricultural land.