Drawing on social cognitive theory and employing a multi-wave questionnaire survey and empirical analysis with data from 305 construction workers, this study establishes a research model to examine the impact of the enterprise-union coupling relationship on construction workers’ safety behavior, while exploring the underlying mechanisms and boundary conditions of this influence. The findings reveal that the enterprise-union coupling relationship positively influences construction workers’ safety behavior, with perceived accident risk probability and perceived accident risk severity serving as mediating factors. Moreover, team safety climate not only positively moderates the effects of the enterprise-union coupling relationship on perceived accident risk probability and perceived accident risk severity, but also further strengthens the indirect effects of the enterprise-union coupling relationship on construction workers’ safety behavior through these two dimensions of risk perception.