(1) Background: Irregular and non-standard work arrangements have become a serious determinant to the health and safety of workers. The aim of this study is to investigate the relationship between shift work and occupational accident absence. A representative Belgian sample considering several sociodemographic and work characteristics is used. (2) Methods: This study is based on the data of the sixth European Working Condition Survey (EWCS). The sample is restricted to 2169 respondents from Belgium. By using multivariate logistic regression modeling techniques and adjusting several confounders, the associations between shift work and occupational accident absence are studied. (3) Results: It is found that about 11.1% of the workers undergo an occupational accident absence. A multivariate regression model demonstrates an increased occupational accident absence risk for workers who have shift work (odds ratio, or OR, 1.92, 95% CI 1.06-3.46). Also, gender and biomechanical exposure were significantly associated with occupational accident absence ((OR 2.07, 95% CI 1.16-3.69) and (OR 2.03, 95% CI 1.14-3.63), respectively). No significant interaction effects are found with gender and age variables. (4) Conclusion: This study confirms that doing shift work is significantly associated with occupational accidents. In order to reduce the significance of occupational accidents, shift work should be limited through national-level policies.