The assessment of solar resources involves the utilization of physical or satellite models for the determination of solar radiation on the Earth’s surface. However, a critical aspect of model validation necessitates comparisons against ground-truth measurements obtained from surface radiometers. Given the inherent challenges associated with establishing and maintaining solar radiation measurement networks—characterized by their expense, logistical complexities, limited station availability and the imperative consideration of climatic criteria for siting—countries endowed with substantial climatic diversity face difficulties in station placement. In this investigation, the measurements of annual solar irradiation, from meteorological stations of the National Weather Service in Mexico, were compared in different regions clustered by similarities in altitude, TL Linke, albedo and cloudiness index derived from satellite images; the main objective is to find the best ratio of annual solar irradiation in a set of clusters. Employing machine learning algorithms, this research endeavors to identify the most suitable model for predicting the ratio of annual solar irradiation and to determine the optimal number of clusters. The findings underscore the efficacy of the L-method as a robust technique for regionalization. Notably, the cloudiness index emerges as a pivotal feature, with the Random Forest algorithm yielding superior performance with a R2 score of 0.94, clustering Mexico into 17 regions.