The main purpose of this study is to investigate the relationships between key sources of air pollutant emissions (sources of energy production, factories which are particularly harmful to the environment, the fleets of cars, environmental protection expenditure) and the main environmental air pollution (SO2, NOx, CO and PM) in Poland. Models based on MLP neural networks were used as predictive models. Global sensitivity analysis was used to demonstrate the significant impact of individual network input variables on the output variable. To verify the effectiveness of the models created, the actual data were compared with the data obtained through modelling. Projected courses of changes in the variables under study correspond with the real data, which confirms that the proposed models generalize acquired knowledge well. The high MLP network quality parameters of 0.99–0.85 indicate that the network generalizes the acquired knowledge accurately. The sensitivity analysis for NOx, CO and PM pollutants indicates the significance of all input variables. For SO2, it showed significance for four of the six variables analysed. The predictions made by the neural models are not very different from the experimental values.