In response to growing environmental threats and the increasing frequency of natural disasters, the sustainable management of hazardous materials (Hazmat) is critical to ensuring national resilience. While Oman has developed policy and procedural frameworks for emergency response, the integration of sustainability principles into Hazmat training remains limited. This study empirically validates a proposed national training framework designed to foster a culture of sustainability among Hazmat stakeholders across logistics, emergency response, and industrial sectors. Building on Oman Vision 2040 and global best practices, the framework incorporates four pillars: (1) policy integration of sustainability in Hazmat protocols, (2) structured, role-based training programs, (3) public–private collaboration, and (4) digital learning and continuous assessment. Secondary data from regional and international sources were analyzed using Partial Least Squares Structural Equation Modeling (PLS-SEM) to test the hypothesized relationships and evaluate the mediating role of sustainability culture. The findings confirm that targeted training programs and integrated policy frameworks significantly enhance sustainability culture and Hazmat response effectiveness. Public–private collaboration showed a positive direct effect, while digital learning tools demonstrated limited impact. This study contributes to advancing green business practices and aligning operational preparedness with Oman Vision 2040 and broader sustainable development goals.