Selenium (Se) is an essential micronutrient for humans, yet its dietary intake is low, mostly due to the low bioavailability in soils and therefore in edible plant tissues. To overcome Se deficiency, the breeding approach (i.e., genetic biofortification), namely in rice, is largely dependent on available Se pools. To ensure the success of genetic biofortification with Se, agronomic biofortification can be accomplished through foliar Se application. Considering this background, the main hypothesis of this work was centered in the foliar application of Se to attain agronomic biofortification of rice crops. This study also aimed to assess the full potential for increasing grain Se concentrations during rice filling, as well as the types of nutrients deposition. An experimental design applying two foliar fertilizers (sodium selenite and sodium selenate) was developed. As test systems, four rice genotypes (Ariete, Albatros, OP1105 and OP1109) were used and the kinetics of micro- and macro-nutrients accumulation and deposition were assessed. Biofortification was performed in field trials for two years with foliar fertilization ranging between 0 and 300 g Se ha−1. At the end of the plant cycle, selenite applications triggered 427- to 884-fold increases in grain Se concentrations among rice genotypes (Albatros > OP1105 > OP1109 > Ariete). The application of selenate also prompted 128- to 347-fold increases in grain Se concentrations in rice crops (Albatros > OP1105 > Ariete > OP1109). Regardless of the foliar fertilizer applied, Se deposition among genotypes occurred throughout the grain without relevant inhibitory effects on yields. In each genotype, micro and macronutrients varied among crop tissues.