This research work proposes a new hybrid framework to assess suitable sites and technical potentials for large-scale solar photovoltaic (PV) systems by integrating two multi-criteria decision-making (MCDM) techniques. The evaluation of sites for PV plants was performed using the MCDM method, taking into account a wide range of variables, including climate, technical, geographical, and economic variables, with factor weights determined using the CRITIC technique. Five Saudi Arabian cities with abundant solar radiation served as illustrations of this study’s framework. For classification, the TOPSIS method was employed to rank the five alternatives. The results show that Riyadh is ranked first with a performance score of 72%, followed by Jeddah with a performance score of 65%, and the remaining three cities, namely, Al Ahsa, Dammam, and Abha scored less than 50%. Lastly, the reliability and robustness of the results obtained were examined using sensitivity analysis. The findings of this study can be used to pinpoint possible places that could be used to build solar power plants and to promote the expansion of generating facilities and electrical grids.