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Circadian cognitive and physical rhythms plus 24 h patterns of accidents and work-related injuries (WRI) have been verified in numerous studies. However, rarely, if ever, have 24 h temporal differences in both work performance and risk of WRI been assessed in the same group of workers. We explored in a homogenous group of French firemen (FM) 24 h patterns of both lag time (LT) response duration to emergency calls for medical help (ECFM) for life-threatening out-of-hospital cardiac arrests (OHCA), used as a non-specific index of work performance, and WRI. Our studies demonstrate rather high amplitude statistically significant 24 h patterns of the two variables. The LT response duration was twice as long -0500 h (slowest response) than -1600 h (fastest response). In the same group of FM, the actual number WRI/h was greatest -1600 h and lowest in the early morning hours. However, the 24 h pattern of the relative risk (RR) of WRIs, i.e., per clock hour number of WRI/(total number of responses to emergency calls x number of FM at risk per response), was very different, the RR being greatest -0200 h and lowest in the afternoon. The 24 h pattern in LT response duration to ECMH for OHCA and RR of WRI was strongly correlated (r = +0.85, P < 0.01), with the nocturnal trough (slowest response) in LT response duration coinciding with the nocturnal peak RR of WRI. These findings indicate the requirement for circadian rhythm-based interventions to improve the nocturnal compromised work performance and elevated risk of WRI of shift-working FM.