Firms’ performance in sustainable development has caused increasing concerns. A key issue is that the environmental characteristics of business managers may be an important driver to promote the sustainable practice of enterprises. This study explores the relationship between ascribed responsibility of managers and green sustainable practice of enterprises by introducing the waste management as mediation variable and green self-efficacy as a moderating variable. A survey was conducted in manufacturing enterprises from the Yangtze River Delta in China in 2019, where 149 valid questionnaires were collected out of 200 surveyed enterprises. Subsequently, the data were analyzed through an analytic hierarchy process. The results show that: (1) ascribed responsibility of managers has a positive impact on green sustainable practices (β = 0.428, p < 0.001), and waste management plays a full mediating role during this process (β = 0.428, p < 0.001); (2) managers' green self-efficacy strengthens the positive impact of waste management on sustainable practices (β = 0.284, p < 0.05); (3) green self-efficacy has positively moderated the indirect effect of managers' ascribed responsibility for sustainable practice through waste management. The research enriches the theories on sustainable practice of enterprises from the perspective of managers’ environmental characteristics and provides insights for enterprises to promote sustainable development practice.