Electric vehicles are rapidly infiltrating the power grid worldwide, initiating an immediate need for a smart charging technique to maintain the stability and robustness of the charging process despite the generation type. Renewable energy sources (RESs), especially photovoltaic (PV), are becoming the essential source for electric vehicle charging points. The stochastic behavior of the PV output power affects the power conversion for regulating the battery charger voltage levels, which influences the battery to overheat and degrade. This study presents a PV standalone smart charging process for off-board plug-in electric vehicles, represented by a small-scale lithium-ion battery based on the multistage charging currents (MSCC) protocol. The charger comprises a DC–DC buck converter controlled by an artificial neural network predictive controller (NNPC), trained and supported by the long short-term memory recurrent neural network (LSTM). The LSTM network model was utilized in the offline forecasting of the PV output power, which was fed to the NNPC as the training data. Additionally, it was used as an alarm flag for any possible PV output shortage during the charging process in the long- and short-term prediction to be supported by any other electricity source. The NNPC–LSTM controller was compared with the fuzzy logic and the conventional PID controllers while varying the input voltage and implementing the MSCC protocol. The proposed charging controller perfectly ensured that the minimum battery terminal voltage ripple and charging current ripple reached 1 mV and 1 mA, respectively, with a very high-speed response of 1 ms in reaching the predetermined charging current stages. The present simulated and experimental results are in good agreement with the previous related work in the literature survey.