We have used first-principles density-functional theory calculations to determine the structural, electronic and optical properties of eight known BaTiO3 phases (Pm3¯m, Amm2, C2221, Pmm2, P4mm, P4/mmm, P63/mmc and R3m). The calculated ground state energies, relative stability and structural parameters of these phases are consistent with the reported theoretical and experimental results. We discuss the band structures, densities of states and chemical bonding of eight phases. Further, we analyze the electron density distributions of cubic BaTiO3 and obtain the molecular-orbital bonding. The optical properties of eight phases have been calculated and the relationships between refractive indices and mass densities have been obtained.