Evapotranspiration (ETo) is one of the most important processes in the hydrologic cycle, with specific application to sustainable water resource management. As such, this study aims to evaluate the predictive ability of a novel method for monthly ETo estimation, using a hybrid model comprising data pre-processing and an artificial neural network (ANN), integrated with the hybrid particle swarm optimisation–grey wolf optimiser algorithm (PSOGWO). Monthly data from Al-Kut City, Iraq, over the period 1990 to 2020, were used for model training, testing, and validation. The predictive accuracy of the proposed model was compared with other cutting-edge algorithms, including the slime mould algorithm (SMA), the marine predators algorithm (MPA), and the constriction coefficient-based particle swarm optimisation and chaotic gravitational search algorithm (CPSOCGSA). A number of graphical methods and statistical criteria were used to evaluate the models, including root mean squared error (RMSE), Nash–Sutcliffe model efficiency (NSE), coefficient of determination (R2), maximum absolute error (MAE), and normalised mean standard error (NMSE). The results revealed that all the models are efficient, with high simulation levels. The PSOGWO–ANN model is slightly better than the other approaches, with an R2 = 0.977, MAE = 0.1445, and RMSE = 0.078. Due to its high predictive accuracy and low error, the proposed hybrid model can be considered a promising technique.