Pigmented rice (Oryza sativa L.) genotypes become increasingly important in the agroindustry due to their bioavailable compounds that have the ability to inhibit the formation and/or to reduce the effective concentration of reactive cell-damaging free radicals. This study aimed at determining the concentrations of free, and bound phytochemicals and their antioxidant potential (DPPH and ABTS assays) as well as the vitamin E and carotenoids contents of non-pigmented and pigmented rice genotypes. The results confirmed that the content of total phenolics and flavonoids contents, as well as the antioxidant capacity (DPPH and ABTS assays) of pigmented rice was several-fold greater than non-pigmented ones (4, 4, 3 and 5 times, respectively). Compounds in the free fraction of pigmented rice had higher antioxidant capacity relative to those in the bound form, whereas the non-pigmented rice cultivars exhibited the opposite trend. Ferulic acid was the main phenolic acid of all rice genotypes, whereas black rice contained protocatechuic and vanillic acids in higher contents than red rice and non-pigmented rice genotypes. For vitamin E (tocopherols and tocotrienols) and carotenoids (lutein, zeaxanthin and β-carotene) contents, no obvious concentration differences were observed between non-pigmented and pigmented rice, with the black rice exhibiting the highest carotenoid content. Overall, pigmented rice genotypes contain a remarkable amount of bioactive compounds with high antioxidant capacity; therefore, they have great potential as a source of bioactives for developing functional food products with improved health benefits.