In order to validate the 12-item Psychological Capital Questionnaire (PCQ-12) and investigate the latent profiles of psychological capital (PsyCap) in Chinese employees, we conducted two studies. In Study 1, we systematically evaluated the psychometric properties of the PCQ-12 among a sample of 755 Chinese employees. The results showed that the PCQ-12 is a reliable and valid tool for measuring Chinese employees’ PsyCap and that it is superior to the 24-item Psychological Capital Questionnaire (PCQ-24). In Study 2, the validated PCQ-12 in Study 1 was used to measure the PsyCap of 1,349 Chinese employees from various organizations and industries, and a person-centered analytic approach was adopted to investigate the latent profiles of PsyCap. The results revealed four distinct profiles with the four components (i.e., efficacy, hope, optimism, and resilience) of PsyCap at similar levels, that is, low, low/moderate, high/moderate, and high. These profiles significantly differ in work outcomes, with the employees in the High PsyCap profile exhibiting the highest levels of work engagement and job satisfaction and the lowest levels of turnover intention, while employees in the Low PsyCap profile exhibit the opposite. Our research demonstrated that the PCQ-12 is a valid and convenient instrument to measure Chinese employees’ PsyCap and offers a fine-grained portrait of their PsyCap in Chinese culture. Moreover, the quantitatively distinct PsyCap profiles found in our research support the unitary structure of PsyCap with its four components converging into an underlying positive capacity and emphasize the synergistic effects of the four components on work outcomes, which informs the current debate over PsyCap and enriches the existing PsyCap literature, thus further shedding light on managerial practice.