Commuting road accidents have a direct impact on workers as well as companies. Therefore, analyzing the characteristics of commuting to and from work and workers’ perceptions of their potential risk is necessary. This study analyzes these factors in a sample of employees in a large Spanish company. A questionnaire was distributed to a total of 665 workers, assessing variables such as means of transport used and preferred in this type of commuting, perceived risks, assessment of preventive measures, involvement in a road accident during commuting, and road safety training received by the company, among others. There is a difference between preferred and used modes of transport, with factors limiting the use of soft modes. People who have experienced an accident on the way to work have a higher risk perception of this type of journey. The time and distance of the journey also have a significant influence on the perceived risk. The most highly rated preventive actions are mainly related to the accessibility and comfort of the workers’ daily commute, which helps minimize the time spent on journeys. This analysis provides relevant information on the social acceptability of different measures for the development and implementation of future actions of the prevention services that contribute to reducing this type of accident and designing strategies to promote more sustainable commuting mobility.