In urban Vehicular Ad Hoc Network (VANET) environments, buildings play a crucial role as they can act as obstacles that attenuate the transmission signal between vehicles. Such obstacles lead to multipath effects, which could substantially impact data transmission due to fading. Therefore, quantifying the impact of buildings on transmission quality is a key parameter of the propagation model, especially in critical scenarios involving emergency vehicles where reliable communication is of utmost importance. In this research, we propose a supervised learning approach based on Artificial Neural Networks (ANNs) to develop a predictive model capable of estimating the level of signal degradation, represented by the Bit Error Rate (BER), based on the obstacles perceived by moving emergency vehicles. By establishing a relationship between the level of signal degradation and the encountered obstacles, our proposed mechanism enables efficient routing decisions being made prior to the transmission process. Consequently, data packets are routed through paths that exhibit the lowest BER. To collect the training data, we employed Network Simulator 3 (NS-3) in conjunction with the Simulation of Urban MObility (SUMO) simulator, leveraging real-world data sourced from the OpenStreetMap (OSM) geographic database. OSM enabled us to gather geospatial data related to the Two-Dimensional (2D) geometric structure of buildings, which served as input for our Artificial Neural Network (ANN). To determine the most suitable algorithm for our ANN, we assessed the accuracy of ten learning algorithms in MATLAB, utilizing five key metrics: Mean Squared Error (MSE), Root Mean Squared Error (RMSE), Mean Absolute Error (MAE), Correlation Coefficient (R), and Maximum Prediction Error (MaxPE). For each algorithm, we conducted fifteen iterations based on ten hidden neurons and gauged its accuracy against the aforementioned metrics. Our analysis highlighted that the ANN underpinned by the Conjugate Gradient With Powell/Beale Restarts (CGB) learning algorithm exhibited superior performance in terms of MSE, RMSE, MAE, R, and MaxPE compared to other algorithms such as Levenberg–Marquardt (LM), Bayesian Regularization (BR), BFGS Quasi-Newton (BFG), Resilient Backpropagation (RP), Scaled Conjugate Gradient (SCG), Fletcher–Powell Conjugate Gradient (CGF), Polak–Ribiére Conjugate Gradient (CGP), One-Step Secant (OSS), and Variable Learning Rate Backpropagation (GDX). The BER prediction by our ANN incorporates the TWO-RAY Ground (TRG) propagation model, an adjustable parameter within NS-3. When subjected to 300 new samples, the trained ANN’s simulation outcomes illustrated its capability to learn, generalize, and successfully predict the BER for a new data instance. Overall, our research contributes to enhancing the performance and reliability of communication in urban VANET environments, especially in critical scenarios involving emergency vehicles, by leveraging supervised learning and artificial neural networks to predict signal degradation levels and optimize routing decisions accordingly.