In this study, density functional theory is used to evaluate the electronic structure of the antimony chalcogenide series. Analysis of the electronic density of states and charge density shows that asymmetric density, or 'lone pairs', forms on the Sb cations in the distorted oxide, sulphide and selenide materials. The asymmetric density progressively weakens down the series, due to the increase in energy of valence p states from O to Te, and is absent for SbTe. The fundamental and optical band gaps were calculated and SbO, SbS and SbSe have indirect band gaps, while Sb Te was calculated to have a direct band gap at Γ. The band gaps are also seen to reduce from SbO to SbTe. The optical band gap for SbO makes it a candidate as a transparent conducting oxide, while SbS and SbSe have suitable band gaps for thin film solar cell absorbers. © 2014 Elsevier Inc.