Training Artificial Neural Networks (ANNs) is a non-trivial task. In the last years, there has been a growing interest in the academic community in understanding how those structures work and what strategies can be adopted to improve the efficiency of the trained models. Thus, the novel approach proposed in this paper is the inclusion of the entropy metric to analyse the training process. Herein, indeed, an investigation on the accuracy computation process in relation to the entropy of the intra-layers’ weights of multilayer perceptron (MLP) networks is proposed. From the analysis conducted on two well-known datasets with several configurations of the ANNs, we discovered that there is a connection between those two metrics (i.e., accuracy and entropy). These promising results can be helpful in defining, in the future, new criteria to evaluate the training process goodness in real-time by optimising it and allow faster detection of its trend.