In some situations, there is no possibility of hazard mitigation, especially if the hazard is induced by water. Thus, it is important to prevent consequences via an early warning system (EWS) to announce the possible occurrence of a hazard. The aim and objective of this paper are to investigate the possibility of implementing an EWS in a small-scale catchment and to develop a methodology for developing a hydrological prediction model based on an artificial neural network (ANN) as an essential part of the EWS. The methodology is implemented in the case study of the Slani Potok catchment, which is historically recognized as a hazard-prone area, by establishing continuous monitoring of meteorological and hydrological parameters to collect data for the training, validation, and evaluation of the prediction capabilities of the ANN model. The model is validated and evaluated by visual and common calculation approaches and a new evaluation for the assessment. This new evaluation is proposed based on the separation of the observed data into classes based on the mean data value and the percentages of classes above or below the mean data value as well as on the performance of the mean absolute error.