In this paper, the optimization of a PV/T (photovoltaic/thermal) active solar still is carried out. Analytical expressions for glass cover temperature, basin temperature, brackish water temperature and fresh water productivity are obtained by writing energy balance for different components of PV/T active solar still. The output electrical power of PV/T active solar still is calculated by four-parameter I–V (current–voltage) model. Objective function in present study is the energy efficiency of PV/T active solar still. A computer simulation program has been developed in order to obtain thermal and electrical parameters, respectively. The simulation results of the present study are in fair agreement with the experimental data of previous literatures. Finally, the optimization of PV/T active solar still has been carried out and the optimized value of mass flow rate, number of PV/T collector and the objective function have been obtained. Furthermore, the effect of various operating parameters on energy efficiency have been investigated.