The voluntary learning behavior of employees indicates the organization may maintain its momentum and competitiveness as a human resource development strategy. Unfortunately, studies concerning voluntary learning behavior are few. Most prior research emphasize the organization’s responsibility to provide supportive environment to facilitate employee learning, yet overlook the obligation for employees to be proactive on their learning. Drawing on the Chinese achievement motivation theory, this study proposes the two-factor of psycho-social work dependency as the antecedent and work involvement as the mediator to influence voluntary learning behavior among employees. Empirical data was collected by a survey of 1,314 employees working in private enterprises in Taiwan. Structural equation modeling was used to validate the proposed model. The results show that the relationships among psycho-social work dependency, work involvement and voluntary learning behavior are validated. Theoretical contribution and practical implications are discussed.