Esports gaming is an area in which videogame players need to cooperate and compete with each other, influencing their cognitive load, processing, stress, and social skills. Here it is unknown to which extent competitive videogame play using a desktop setting can affect the physiological responses of players’ autonomic nervous system. For such, we propose a study where we have measured distinct electrodermal and cardiac activity metrics over competitive players during several League of Legends gameplay sessions in a Esports stadium. We mainly found that game performance (whether winning or losing the game) significantly affects both electrodermal and cardiac activity, where players who lost the game showed higher stress-related physiological responses, as compared to winning players. We also found that important specific in-game events such as “Killing”, “Dying” or “Destroying Turret” significantly increased both electrodermal and cardiac activity over players more than other less-relevant events such as “Placing Wards” or “Destroying Turret Plates”. Finally, by analyzing activity over player roles we found different trends of activity on these measurements, this could foster the exploration on human physiology with a higher set of participants in future Esports studies.