Spain is the EU member country with the third highest total number of accidents in work and has the third highest incidence rate. We have performed a descriptive analysis of occupational accidents in the Community of Madrid (Spain) between 2005 and 2013 to study the impact of air quality on the prevalence of occupational accidents, clarifying how vulnerable to air pollution outdoor workers are. In order to evaluate the association between each air pollutant and work accidents, a quasi-Poisson generalized additive model was fitted. The accident rate followed a downward and statistically significant trend (p = 0.001). The year with the highest accident rate was 2006, with 4981 occupational accidents per 100,000. Occupational accidents follow a temporary pattern (there are differences in the number of accidents according to the month of the year and to the day of the week). Exposure to PM10 and NO2 increases the risk of having an accident at work, especially for outdoor workers. An increase of 10 μg/m3 in daily concentration resulted in increases in accidents for outdoor workers of 2.5% for PM10 and 6.4% for NO2.