The electronic properties and the low environmental impact of Cu 3 BiS 3 make this compound a promising material for low-cost thin film solar cell technology. From the first principles, the electronic properties of the isoelectronic substitution of S by O in Cu 3 BiS 3 have been obtained using two different exchange–correlation potentials. This compound has an acceptor level below the conduction band, which modifies the opto-electronic properties with respect to the host semiconductor. In order to analyze a possible efficiency increment with respect to the host semiconductor, we have calculated the maximum efficiency of this photovoltaic absorber material. Copyright © 2012 John Wiley & Sons, Ltd.