This study explores whether employees’ perceptions of corporate human resource practices (training and rewards), and employees’ perceptions of corporate sustainability responsibility, affect their adoption of sustainable behaviors. In the past, there have been relevant studies to explore the impact of corporate sustainability education and training and sustainable rewards on employees’ sustainable behavior. However, the results were not significant. Thus, this study constructed a prediction model to examine the relationship between the abovementioned factors, moving beyond the previous related studies. Employees of Common Wealth Magazine’s Sustainable Citizenship Award-winning companies were selected as the research objects to verify whether employees’ perception of corporate sustainable responsibility has a mediating effect. The instrument was developed from a literature review and related survey items, which consisted of 35 items and four dimensions. The instrument’s validity and reliability passed the required standards. Through judgmental sampling, a total of 345 valid responses were collected. Through hierarchical regression analysis, we found that sustainability training and sustainable rewards have a significant impact on employees’ sustainable behavior. The scientific value of this study is the contribution of the framework model for employees’ perception of corporate sustainable responsibility, which has a mediating effect. It provides practical evidence that employees’ perception of corporate sustainable responsibility plays a partial mediation role. In general, facilitating employees’ sustainable behavior can be achieved through environmental and social aspects, as well as cooperative governance, to further enhance employees’ internal and external roles in relation to sustainable behavior.