During COVID-19 pandemic peaks, healthcare professionals are a frontline workforce that deals with death on an almost daily basis and experiences a marked increase in workload. Returning home is also associated with fear of contaminating or be contaminated. An obvious consequence is stress accumulation and associated risks, especially in caregivers in mobility and possibly in human resource teams managing mobility. Here, during the second pandemic peak, we designed a 15-min testing procedure at the workplace, combining HADS and Brief COPE questionnaires with heart rate variability (HRV) recordings to evaluate psychophysiological status in four groups: caregivers in mobility (MOB); human resources teams managing mobility (ADM); caregivers without mobility (N-MOB); and university researchers teaching online (RES). Anxiety, depression, coping strategies, vagally-mediated heart rate regulation, and nonlinear dynamics (entropy) in cardiac autonomic control were quantified. Anxiety reached remarkably high levels in both MOB and ADM, which was reflected in vagal and nonlinear HRV markers. ADM maintained a better problem-solving capacity. MOB and N-MOB exhibited degraded problem-solving capacity. Multivariate approaches show how combining psychological and physiological markers helps draw highly group-specific psychophysiological profiles. Entropy in HRV and problem-solving capacity were highly relevant for that. Combining HADS and Brief COPE questionnaires with HRV testing at the workplace may provide highly relevant cues to manage mobility during crises as well as prevent health risks, absenteeism, and more generally malfunction incidents at hospitals.