Leadership emergence (LE), the process by which individuals are recognized as leaders within their groups, has a significant impact on group performance. However, the physiological processes underlying LE remain largely unexplored. This study investigates the role of objective physiological measures, specifically electrodermal activity (EDA), in uncovering the mechanisms that contribute to LE. EDA reflects sympathetic nervous system activation and provides real-time insights into processes such as emotional arousal, attention, and vigilance—factors previously linked to LE. Participants (N = 144), nested in 48 three-person groups, completed a group decision-making task while their physiological data were continuously recorded. Two EDA components were analyzed: lability (baseline activity) and interactive EDA (dynamic responses during group interactions). LE was assessed using peer rankings conducted at the end of the group interaction. Multilevel Poisson regression analyses revealed that both mean baseline and interactive EDA positively predicted LE, even after controlling for variables such as gender, age, intelligence proxies, and other relevant factors. These findings suggest that processes associated with elevated EDA levels, such as emotional arousal, attention, and vigilance, promote the emergence of leaders in small groups. This study highlights the value of physiological measures like EDA in overcoming the limitations of traditional self-report tools, offering deeper and more accurate insights into the mechanisms driving LE.