High-efficiency non-isolated converters play a predominant role in electric vehicle on-board chargers to enhance the sustainability of EV charging stations. A novel single-switch configuration connected in a new parallel structure offering a higher efficiency than recently reported topologies is introduced in this article. A PV source powered single switch–switched capacitor–single inductor (SS–SC–SL) arrangement employing an intelligent, robust controller (MPC) is proposed to build a sustainable framework for electric vehicles. Notable features of this topology include improved voltage regulation, a high output gain, and maintaining a ripple-free continuous load current at a nominal duty cycle range which is commonly applicable for electric vehicle on-board chargers. In addition, several factors are included, as follows: design considerations, theoretical analysis, converter performance in CCM, and comparison with existing configurations. The converter simulation results are executed using the MATLAB software 2022a, and to verify the system performance, an experimental setup of 150 W is built and tested. The hardware results of a higher efficiency at 96.9% and a ripple-less continuous load current are achieved and validated in the laboratory.