Psychological thriving is crucial for the sustainable well-being and continuous growth of employees in the workplace. This study aims to explore the concept, measurement, and heterogeneity of dualistic psychological thriving at work to promote sustainable vitality and learning among employees. In Study 1, we identified psychological thriving at work as a second-order dualistic construct, encompassing the positive psychological state in which individuals experience vitality and learning in their current work and hold high expectations for their future work. This construct consists of two dimensions: psychological thriving of work experience and psychological thriving of work development. In Study 2, we conducted exploratory factor analysis and second-order confirmatory factor analyses using two independent samples, providing empirical evidence for the second-order dualistic structure of psychological thriving at work. Subsequently, we developed a comprehensive scale to measure dualistic psychological thriving at work and assessed its criterion validity by examining its relationship with workplace friendship and work autonomy. In Study 3, we investigated the overall levels and pursuit preferences of dualistic psychological thriving at work among different generations. The findings revealed significant differences in the overall levels and pursuit preferences of dualistic psychological thriving at work across generations. Post-1990s employees exhibited the highest overall level of dualistic psychological thriving at work, while post-1970s employees had the lowest. Moreover, post-1990s employees were more inclined to pursue psychological thriving of work experience, whereas post-1980s employees tended to seek psychological thriving of work development. No significant differences were found among post-1970s employees.