Despite the prevalent stereotype that former entrepreneurs are undesirable employees due to a high likelihood of quitting, little research has empirically verified its accuracy. With a growing population of former entrepreneurs in the workforce, it has become more important than ever to understand whether, when, and which former entrepreneurs may or may not be likely to quit their post‐entrepreneurship employment. We used a sample of nationally representative 20‐year data from Australia to examine how timing of prior entrepreneurial experience relative to a focal wage job relates to voluntary turnover via a serial mediation by entrepreneurial intention and turnover intention. Results showed that employees with entrepreneurial experience in their second most recent job spell were more likely to develop entrepreneurial intention and turnover intention in sequence, which, in turn, increased quitting risk relative to employees without entrepreneurial experience in the same job spell. However, we did not find evidence for such differences between employees with and without entrepreneurial experience in their most recent job spell. Moreover, the serial mediation effect holds among men but not women. These findings highlight the important role of timing in the relationship between of entrepreneurial experience and post‐entrepreneurship employment attitude and behavior. Theoretical contributions and practical implications are discussed.