Considering the Social Network Analysis approach and based on the creation of mathematical models, the aim of this study is to analyze the players’ interactions of professional football teams in critical moments of the game. The sample consists in the analysis of a 2019/2020 season UEFA Champions League match. The mathematical models adopted in the analysis of the players (micro analysis) and the game (macro analysis) were obtained through the uPATO software. The results of the networks indicated a performance pattern trend more robust in terms of the mathematical model: Network Density. As far as it concerned, we found that the Centroid Players had a decisive role in the level of connectivity and interaction of the team. Regarding the main critical moments of the game, the results showed that these were preceded by periods of great instability, obtaining a differentiated performance in the following mathematical models: Centrality, Degree Centrality, Closeness Centrality, and Degree Prestige. We concluded that the networks approach, in concomitance with the dynamic properties of mathematical models, and the critical moments of the game, can help coaches to better evaluate the level of interaction and connectivity of their players toward the actions imposed by opponents.