WAAM has emerged as a promising technique for manufacturing medium- and large-scale metal parts due to its high material deposition efficiency and automation level. However, its high heat accumulation and complex thermal evolution strongly affect the resulting microstructures and mechanical properties. The heterogeneous and unpredictable nature of these properties hinder the widespread application of WAAM in the steel construction industry. In this study, an artificial neural network (ANN) hardness model is developed, based on a thermal–metallurgical model for mild steel. The objective is to establish non-linear relationships between the input process parameters and the desired output, i.e., hardness. The thermal–metallurgical model utilizes a well-distributed heat source model, a death-and-birth algorithm, and a metallurgical model to simulate the temperature field and to calculate the microstructure phase fraction. The temperature prediction errors at four thermocouple positions are mostly below 20%. Because of the limited experimental data, twenty-five simulation experiments are performed using the L25 orthogonal array based on the Taguchi method. The analysis of variance (ANOVA) reveals that the travel speed has the greatest impact on hardness. With the dataset from the thermal–metallurgical model, an ANN model to predict hardness is developed. A comparison to experimental data shows excellent performance and accuracy, with the Mean Absolute Percentage Error (MAPE) of ANN predictions within 10% of the targeted hardness.