Firefighters face a high-risk potential, thus their psychological ability to cope with critical or traumatic events is a crucial characteristic. This study examines correlations between cardiac autonomic modulation, risk-taking behavior, and resilience in professional firefighters. Twenty male professional firefighters underwent a 20 min beat-to-beat heart rate (HR) monitoring at baseline in the morning upon awakening, then before, during and after a realistic deployment in a container, systematically set on fire. Risk-taking behavior, resilience, and subjective stress were assessed by specific validated tools after deployment: the Risk-taking Scale (R-1), the Resilience Scale (RS-13), and the multi-dimensional NASA-Task Load Index. The cardiac autonomic modulation at rest and in response to stress was assessed by classic indexes of heart rate variability (HRV) as RMSSD and LF/HF ratio. Results showed that: (i) risk-taking behavior correlated with a withdrawal in vagal indices, shifted the baseline sympathovagal balance toward sympathetic predominance (LF/HF ratio r(8) = 0.522, p = 0.01), and increased mean HR both in baseline and during physical exercise (r(8) = 0.526, p = 0.01 and r(8) = 0.445, p = 0.05, respectively); (ii) resilience was associated with higher vagal indices (RMSSD r(18) = 0.288, p = 0.04), and with a baseline sympathovagal balance shifted toward parasympathetic predominance (LF/HF ratio r(18) = -0.289, p = 0.04). Associations of risk-taking behavior and resilience with cardiac autonomic modulation could be demonstrated, showing that HRV may be a valuable monitoring tool in this specific population; however further studies are warranted for validation.