The paper presents an in-depth analysis of a novel scheme for the sustainable mobility, based on electric vehicles, photovoltaic energy and electric energy storage systems. The work aims to analyse such innovative system, putting in evidence its advantages in comparison to a conventional one, based on the grid-to-vehicle technology. The study also provides interesting guidelines for potential users and system designers. Two case studies are presented: i) the taxi fleet of the city centre of Naples and ii) the cargo vans of the city of Salerno; both towns are in Southern Italy. For each case, the hourly power consumption of the vehicles was evaluated, as a function of the daily trip length. An accurate procedure was implemented to select the sites suitable for the installation of the charging stations, including a photovoltaic field and an electric storage system. A comparison was also performed between two different electric storage technologies: lead-acid and lithium-ion battery. The case studies were analysed by means of a detailed dynamic simulation model, developed in TRNSYS. A sensitivity analysis was also performed, to evaluate how different values of the most important design and operating parameters affect the system overall performance. It was found that the results are mostly affected by solar field area, capacity of the energy storage system and investment cost. The comparison between the two selected storage technologies did not exhibit significant differences. For both the cases investigated, it was found that, during the summer, solar energy covers an important amount of the total energy demand. On the contrary, in winter the amount of energy provided by the public electric grid was high. From an economic point of view, assuming a lithium-ion battery capital cost equal to 90 €/kWh, acceptable pay-back periods (about 6 years) were obtained, for both the applications considered.