Recently, many researchers have proved that the electrification of the transport sector is a key for reducing both the emissions of green-house pollutants and the dependence on oil for transportation. As a result, Plug-in Hybrid Electric Vehicles (or PHEVs) are receiving never before seen increased attention. Consequently, large-scale penetration of PHEVs into the market is expected to take place in the near future, however, an unattended increase in the PHEVs needs may cause several technical problems which could potentially compromise the stability of power systems. As a result of the growing necessity for addressing such issues, topics related to the optimization of PHEVs’ charging infrastructures have captured the attention of many researchers. Related to this, several state-of-the-art swarm optimization methods (such as the well-known Particle Swarm Optimization (PSO) or the recently proposed Gravitational Search Algorithm (GSA) approach) have been successfully applied in the optimization of the average State of Charge (SoC), which represents one of the most important performance indicators in the context of PHEVs’ intelligent power allocation. Many of these swarm optimization methods, however, are known to be subject to several critical flaws, including premature convergence and a lack of balance between the exploration and exploitation of solutions. Such problems are usually related to the evolutionary operators employed by each of the methods on the exploration and exploitation of new solutions. In this paper, the recently proposed States of Matter Search (SMS) swarm optimization method is proposed for maximizing the average State of Charge of PHEVs within a charging station. In our experiments, several different scenarios consisting on different numbers of PHEVs were considered. To test the feasibility of the proposed approach, comparative experiments were performed against other popular PHEVs’ State of Charge maximization approaches based on swarm optimization methods. The results obtained on our experimental setup show that the proposed SMS-based SoC maximization approach has an outstanding performance in comparison to that of the other compared methods, and as such, proves to be superior for tackling the challenging problem of PHEVs’ smart charging.