In this paper, the problem of simultaneous charging of Electrical Vehicles (EVs) in distribution networks (DNs) is examined in order to depict congestion issues, increased power losses, and voltage constraint violations. To this end, this paper proposes an optimal EV charging schedule in order to allocate the charging of EVs in non-overlapping time slots, aiming to avoid overloading conditions that could stress the DN operation. The problem is structured as a linear optimization problem in GAMS, and the linear Distflow is utilized for the power flow analysis required. The proposed approach is compared to the one where EV charging is not optimally scheduled and each EV is expected to start charging upon its arrival at the residential charging spot. Moreover, the analysis is extended to examine the optimal siting of small-sized residential Photovoltaic (PV) systems in order to provide further relief to the DN. A mixed-integer quadratic optimization model was formed to integrate the PV siting into the optimization problem as an additional optimization variable and is compared to a heuristic-based approach for determining the sites for PV installation. The proposed methodology has been applied in a typical low-voltage (LV) DN as a case study, including real power demand data for the residences and technical characteristics for the EVs. The results indicate that both the DN power losses and the voltage profile are further improved in regard to the heuristic-based approach, and the simultaneously scheduled penetration of EVs and PVs could yield up to a 66.3% power loss reduction.