Electric vehicles (EV) are considered as a better mode of transportation due to its un-contaminating nature. EV attains efficient sustainable charging system when incorporating with photovoltaic (PV) system, although the minimal output from PV is unable to satisfy the need of EVs. Henceforth, this paper proposed a novel coupled-inductor (CL)-based interleaved boost converter (IBC) along with optimized radial basis function neural network (RBFNN) maximum power point tracking (MPPT) technique. The CL-IBC enhances the power density and efficiency of the single-phase grid system with minimal voltage stress by increasing the voltage gain. Subsequently, incorporating butterfly-optimized RBFNN controller efficiently tracks the highest possible energy from solar module under varying weather conditions. The outcomes for the proposed topology are evaluated and simulated from the MATLAB software, which demonstrates that the proposed converter achieves higher efficiency value of 91% with reduced total harmonic distortion (THD) of 5.92% and the MPPT approach attains higher tracking efficiency with quick convergence rate.