As the soft power of enterprises, the impact of corporate culture on employee performance and its intrinsic psychological mechanism has been paid close attention to by researchers. Based on the existing research, this paper discusses the impact of corporate culture on the psychological capital of employees and the intermediate role of psychological capital between corporate culture and job performance. 377 employees of a large state-owned petrochemical enterprise were investigated. The results show that: 1) the corporate culture has a significant positive impact on the dimensions of psychological capital (self-efficacy, optimism, hope, resilience) and work performance; 2) psychological capital take a part of the intermediary effect between the corporate culture and work performance. The results of this study have some implications for the management practice of using corporate cultural influence to promote employees' psychological capital and improve performances.