Objectives: A case-control study was carried out to identify driving behaviors associated with the risk of on-duty road accident and to compare driving behaviors according to the type of journey (on duty, commuting, and private) for on-duty road accident victims. Methods: Cases were recruited from the Rhône Road Trauma Registry between January 2004 and October 2005 and were on duty at the time of the accident. Control subjects were recruited from the electoral rolls of the case subjects’ constituencies of residence. Cases’ and controls’ driving behavior data were collected by self-administered questionnaire. A logistic regression was performed to identify behavioral risk factors for on-duty road accidents, taking into account age, sex, place of residence, road accident risk exposure, socio-occupational category, and type of road user. A second analysis focused specifically on the case subjects, comparing their self-assessed usual behaviors according to the type of journey. Results: Significant factors for multivariate analysis of on-duty road accidents were female gender, history of on-duty road accidents during the previous 10 years, severe time pressure at work, and driving a vehicle not belonging to the driver. On-duty road accident victims reported behavioral risk factors more frequently in relation to driving for work than driving for private reasons or commuting: nonsystematic seat belt use, cell phone use at least once daily while driving, and history of accidents with injury during the previous 10 years. Conclusions: This study provides knowledge on behavioral risk factors for on-duty road accidents and differences in behavior according to the type of journey for subjects who have been on-duty road accident victims. These results will be useful for the design of on-duty road risk prevention.