The Food and Agriculture Organization has proposed the current version of the Penman–Monteith method (FAO56-PM) as the standard for calculating reference evapotranspiration (ET0); however, high meteorological data requirements limit its application in many areas. There is thus an urgent need to identify the best alternative empirical method to accurately calculate ET0 in regions that lack sufficient meteorological data. In this study, three temperature-based methods and five radiation-based methods were evaluated using ET0 values generated using the FAO56-PM method in 36 agricultural zones in China based on meteorological data from 823 stations, measured between 2011 and 2020. The results showed that the optimal temperature-based method and radiation-based method differed for different agricultural zones, and no one temperature method or radiation method could be suitable for all agricultural zones. The eight empirical methods were regionally calibrated to improve the ET0 calculation accuracy in the different zones. The relationship between the optimal methods and climatic conditions showed that the most reliable empirical method could be selected according to the local annual mean temperature and aridity index. The results provide useful guidance for the selection of reliable empirical ET0 methods in agricultural zones outside China.