The psychological mechanism of the boundary conditions between overqualification and employees’ behavior remain unclear. Therefore, we conducted a survey with 276 employees by modifying a previously validated instrument to assess perceived overqualification, job crafting, work alienation, and psychological resilience. Results of correlation analysis of the collected data revealed that perceived overqualification had a negative impact on job crafting (i.e., employees’ physical and cognitive changes within the task or relational boundaries of work), but a positive impact on work alienation, and that work alienation played a mediating role between perceived overqualification and job crafting. Additionally, the negative effect of overqualification on job crafting that was mediated by work alienation was buffered when psychological resilience was high rather than low. Theoretical and practical implications about management of qualified employees in organizations are discussed.