Innovation is crucial for enterprises to maintain a sustainable competitive advantage. Reverse mentoring, as an emerging mentoring practice that promotes knowledge and idea exchange between junior employees and senior colleagues, is regarded as a crucial element in driving overall innovation within organizations and is gradually attracting the attention of scholars. However, empirical research on its potential benefits is still relatively scarce. Based on the cognitive appraisal theory of stress, this study investigates the relationship and internal mechanisms between reverse mentoring and employees’ innovative behaviors through a two-period follow-up survey of 528 employees in China’s science and technology-based enterprises. The hypotheses were verified using structural equation modeling and bootstrap analysis, and the findings indicated that reverse mentoring positively influenced employees’ innovative behaviors. Simultaneously, challenge stress appraisal and continuous learning serve as chain mediators between reverse mentoring and employees’ innovative behaviors. This study provides valuable references for organizations to effectively implement reverse mentoring practices and foster innovation, offering a new pathway for sustainable innovation among enterprise employees.