Nowadays, the optimum technical design of Photovoltaic and Battery Energy Storage System (PV-BESS) is crucial for ensuring their economic feasibility, which implies the minimum cost sizing of the system components. In fact, a good design of the off-grid PV-BESS system allows the outages to be avoided, ensures the quality and the security of the power supply, from the one hand, and guarantees the economic and environmental benefits, from the other one. In this context, this paper analyses the technical and economic viability of an off-grid PV-BESS for Charging Electric Vehicles (EVs). The study is performed using HOMER software and meteorological data of Madrid, Spain, and by applying the load shifting principle. In order to verify the effectiveness and rentability of the studied system, its efficiency has been compared to grid- connected charging points, considering the environmental aspects. The obtained results demonstrate that the off-grid PV-BESS are technically and economically viable and reliable. Moreover, they are profitable while allowing a significant reduction of the air pollution.