Electro-oxidation with boron-doped diamond (BDD) electrodes has been demonstrated as an effective technology that achieves the complete mineralization of very different types of wastewater pollutants. Its main drawback is the high primary energy demand. Direct connection of photovoltaic (PV) modules to the electrochemical reactor is carried out to reduce the non-renewable primary energy consumption of the technology. The aim of this work is to model the so-called photovoltaic solar electro-oxidation (PSEO) process. For this purpose, experiments were performed with different wastewaters (urban and synthetic) at different scales (laboratory and pilot plant). A first order kinetic respecting total organic carbon (TOC) for the mineralization rate is concluded. PV modules performance is described in terms of a linear relationship between the current generated and the solar irradiance. Moreover, the definition of two efficiencies that describe the process performance is possible using model equations: current efficiency, eta(c), and energy conversion efficiency, eta(e). (C) 2011 Elsevier B.V. All rights reserved.