An accurate computational approach for the prediction of pan evaporation over daily time horizons is a useful decisive tool in sustainable agriculture and hydrological applications, particularly in designing the rural water resource systems, water use allocations, utilization and demand assessments, and the management of irrigation systems. In this study, a hybrid predictive model (Multilayer Perceptron-Firefly Algorithm (MLP-FFA)) based on the FFA optimizer that is embedded within the MLP technique is developed and evaluated for its suitability for the prediction of daily pan evaporation. To develop the hybrid MLP-FFA model, the pan evaporation data measured between 2012 and 2014 for two major meteorological stations (Talesh and Manjil) located at Northern Iran are employed to train and test the predictive model. The ability of the hybrid MLP-FFA model is compared with the traditional MLP and support vector machine (SVM) models. The results are evaluated using five performance criteria metrics: root mean square error (RMSE), mean absolute error (MAE), Nash-Sutcliffe efficiency (NS), and the Willmott’s Index (WI). Taylor diagrams are also used to examine the similarity between the observed and predicted pan evaporation data in the test period. Results show that an optimal MLP-FFA model outperforms the MLP and SVM model for both tested stations. For Talesh, a value of WI = 0.926, NS = 0.791, and RMSE = 1.007 mm day−1 is obtained using MLP-FFA model, compared with 0.912, 0.713, and 1.181 mm day−1 (MLP) and 0.916, 0.726, and 1.153 mm day−1 (SVM), whereas for Manjil, a value of WI = 0.976, NS = 0.922, and 1.406 mm day−1 is attained that contrasts 0.972, 0.901, and 1.583 mm day−1 (MLP) and 0.971, 0.893, and 1.646 mm day−1 (SVM). The results demonstrate the importance of the Firefly Algorithm applied to improve the performance of the MLP-FFA model, as verified through its better predictive performance compared to the MLP and SVM model.