Increasing the share of renewable energy sources in global electricity production is one of the main goals of sustainable development and environmental protection. Solar energy in many parts of the world has a great potential that is still underutilized. Serbia is one of the European countries with significant solar potential and conditions for the construction of solar power plants. Before installing photovoltaic panels and construction of solar power plants, the most suitable areas must be identified. This is the first step in which many environmental and socio-economic factors are considered to identify the most suitable areas and make efficient use of solar energy. The territory of the city of Kraljevo is the largest administrative unit in Serbia, which has a certain potential that has not been used so far. Using geographic information systems (GIS) and the Best–Worst Method (BWM), six natural and anthropogenic factors that have a significant impact on the final selection of suitable locations were determined and evaluated. By assigning weighting coefficients and processing six thematic maps in GIS, a synthesis map of amenities was created. On the territory of the city of Kraljevo, about 6.98% of the area is most suitable, while 25.23% is suitable for the construction of solar power plants. This is the first study for Kraljevo that integrates GIS-BWM for the needs of solar energy potential. The obtained results provide an adequate geospatial representation of the most suitable locations, which can be useful to decision-makers in the proper utilization of solar energy.