Selenium (Se) is an essential trace element that has various beneficial effects for human healthy. However, the effects of different Se forms and concentrations on growth and development, photosynthetic characteristics and antioxidant capacity are still unclear with regard to the dual grain-and-feed dual-use of ratoon rice (RR). In this study, three concentrations of three different Se forms were applied to RR using the foliar spraying method, and the results showed that Se treatment can increase the Se content of rice grain and straw. All the Se treatments improved the photosynthetic indexes and activities of antioxidant enzymes. The Se and trace elements contents, and the percentages of organic Se and protein Se of brown rice were found to be similar in all three Se forms. A higher organic Se content was found in the grain by spraying sodium selenite and Se-Met, in which the resistant starch (RS) content was increased with the increase in amylose content in grains. The main Se species in the grain was SeMet and the SeMeCys was found only with SeMet treatments. The grain quality showed that all three Se forms increased the consistency of gelatinization. Our study indicated that exogenous Se could improve the nutritional quality of both grain and straw by improving photosynthetic traits and antioxidant enzyme activities, especially sodium selenite and Se-Met. These results underscore the potential of foliar biofortification to enhance the functional component contents of RR grains and provide an insight into the Se enrichment of ratoon rice.