The energy consumption of buildings presents a significant concern, which has led to a demand for materials with better thermal performance. Thermal conductivity (TC), among the most relevant thermal properties, is essential to address this demand. This study introduces a methodology integrating a Multilayer Perceptron (MLP) and a Generative Adversarial Network (GAN) to predict the TC of concrete based on its mass composition and density. Three scenarios using experimental data from published papers and synthetic data are compared and reveal the model’s outstanding performance across training, validation, and test datasets. Notably, the MLP trained on the GAN-augmented dataset outperforms the one with the real dataset, demonstrating remarkable consistency between the model’s predictions and the actual values. Achieving an RMSE of 0.0244 and an R2 of 0.9975, these outcomes can offer precise quantitative information and advance energy-efficient materials.