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Commuting road traffic collisions (RTCs) are one of the main causes of occupational death worldwide, including Italy. Among the prominent yet relatively understudied personal risk factors in the subpopulation of workers, there is the use of psychoactive substances. Since the phenomenon of driving under alcohol and drugs effects in the commuter sub-population has so far been poorly studied, we carried out a study by comparing results obtained from the analysis of commuters and non-commuters. The percentage of commuting RTCs victims was 10.4% out of all the RTCs. Commuter victims were mostly men, 51–60 years-old, motorcyclists (32.1%) or car drivers (28.6%), employees, deceased during Fridays and Saturdays, in the afternoon (35.7%) and in the evening (32.1%). It was possible to perform toxicological analyses in 60.7% of commuter cases: approximately 40% tested positive, always and only for ethanol (median Blood Alcohol Concentration, BAC, of about 1.03 g/L). Values above the legal limit were observed in 23.5% of the toxicological samples analyzed from commuter accidents. Our findings contribute to bridging the gap in knowledge in the area of RTCs and commuting and emphasize the importance of carrying out toxicological investigations, with possible repercussions on both insurance issues and public health strategies, which are relevant for analyzing the phenomenon structurally.