The objective of this work is to increase the open circuit voltage of CuGaSe2(CGS)-based solar cells without decreasing their efficiency. For that, the interface between the p-type CGS absorber and the n-type CdS/ZnO window layer is compared using three different recipes for the growth of the buffer layer. Results show the importance of the adaptation of the CdS buffer layer to the CuGaSe2 absorber film. A maximum open circuit voltage of 922 mV is achieved for the devices when using 60ºC as the chemical bath temperature and a low thiourea concentration. Drive-level capacitance profiling, external quantum efficiency and temperature dependent current-voltage measurements reveal a better quality of the CdS/CuGaSe2 interface for this buffer layer deposition conditions. Factors such as the larger depletion region width and the lower doping level, reducing the tunnelling component, are pointed out as responsible of the higher Voc.