An organizational ethical climate enhances the degree of collaboration and cohesion among employees and facilitates the development and interests of organizations. Such roles lead to organizational sustainable development and survival. Therefore, the importance of ethical climate in organizations is becoming increasingly apparent. In this background, this study aims to explore whether an organizational ethical climate can improve whistleblowing behavior and the mediating role of organizational identification in promoting whistleblowing behavior. Most previous studies have only focused on the mediating or moderating role of the model. This study expands the research field, adds the dual moderation of person–organization value congruence and leader ethical behavior, and verifies two moderated mediation models. Overall, the purpose of this study is to determine the behavior of employees under the influence of an organizational ethical climate and, on this basis, propose suggestions for strengthening organizational ethical climate, expanding the scope of research on organizational climate and providing a theoretical basis for related research. In order to achieve the research goals, the data were collected from 344 Chinese SMEs for empirical analysis. The results showed that an organizational ethical climate has no direct impact on whistleblowing behavior but could have a positive effect on whistleblowing formation through the mediating variable of organizational identification. In addition, person–organization value congruence and leader ethical behavior significantly moderated the mediating role of organizational identification between organizational ethical climate and whistleblowing behavior. Finally, the directions that can contribute to future research were suggested.