Large-scale photovoltaic (PV) power plants may affect the hydrological cycle in all its components. Among the various components, evapotranspiration is one of the most important. As a preliminary step for assessing the impacts of PV plants on evapotranspiration, in this study, we performed an evaluation study of methods for estimating reference evapotranspiration (ETo). FAO and ASCE recommend the Penman–Monteith (PM) method for the estimation of ETo when the data for all involved variables are available. However, this is often not the case, and different empirical methods to estimate ETo, requiring mainly temperature data, need to be used. This study aimed at assessing the performance of different temperature- and radiation-based empirical ETo estimation methods against the standardized PM ETo method in an experimental photovoltaic power plant in Piazza Armerina, Sicily, Italy, where a meteorological station and a set of sensors for soil moisture were installed. The meteorological data were obtained from the Lab from July 2019 to end of January 2022. By taking the ETo estimations from the PM method as a benchmark, the study assessed the performance of various empirical methods. In particular, the following methods were considered: Hargreaves and Samani (HS), Baier and Robertson (BR), Priestley and Taylor (PT), Makkink (MKK), Turc (TUR), Thornthwaite (THN), Blaney and Criddle (BG), Ritchie (RT), and Jensen and Haise (JH) methods, using several performance metrics. The result showed that the PT is the best method, with a Nash–Sutcliffe efficiency (NSE) of 0.91. The second method in order of performance is HS, which, however, performs significantly worse than PT (NSE = 0.51); nevertheless, this is the best among methods using only temperature data. BG, TUR, and THN underestimate ETo, while MKK, BG, RT, and JH showed overestimation of ETo against the PM ETo estimation method. The PT and HS methods are thus the most reliable in the studied site.