Based on the new-type leadership in the innovation-driven era, this study constructs the influence mechanism of secure-base leadership on employees’ proactive innovation behavior from the perspective of social information processing theory. Then, using the questionnaire data collected from 331 employees in startup companies, it empirically tests the theoretical model through hierarchical regression and the Bootstrap method. The results show that: secure-base leadership has a positive impact on employees’ proactive innovation behavior; secure-base leadership stimulates employees’ proactive innovation behavior by making them perceive that they are trusted by their superiors; employees’ proving goal orientation and learning goal orientation positively moderate the relationship between secure-base leadership and perceived superior trust, as well as the indirect effect of secure-base leadership on proactive innovation behavior through perceived superior trust; while employees’ avoidance goal orientation negatively moderates the relationship between secure-base leadership and perceived superior trust, as well as the indirect effect of secure-base leadership on proactive innovation behavior through perceived superior trust. The research findings reveal the empirical evidence that secure-base leadership can stimulate employees’ proactive innovation behavior at the micro-level, and also provide useful insights for enterprises to optimize secure-base leadership and cultivate employees’ proactive innovation behavior in practice.