This paper presents first-principle studies on the photoelectric properties of various Bi2O3 polymorphs. The intrinsic reason of different photocatalytic activities was revealed by electronic structures and optical features. Results showed that for α, β, and γ-Bi2O3, the top of valence bands were mainly constructed by Bi6s and O2p orbitals, and the bottom of conduction bands were dominantly composed by Bi6p orbital. However, two intermediate bands were found at the Fermi level for γ-Bi2O3, which leads to a two-step transition from the top of valence band to the bottom of conduction band and facilitates electron transition under irradiation. Absent forbidden gap was found in δ-Bi2O3, resulting in a semimetallic character due to its intrinsic oxygen vacancy and high ionic conductivity. Moreover, the optical properties of α, β, and γ-Bi2O3 were investigated by absorption spectrum, dielectric constant function, and energy loss spectroscopy. We concluded that the photocatalytic activities followed in the order of γ-Bi2O3 > β-Bi2O3 > α-Bi2O3, in accord with the experimental report. Calculation results illustrated the experimental observations and provided a useful guidance in exploring promising visible-light semiconductor photocatalysts.