The present study investigates the relationship between positive psychological capital (PsyCap) and innovative work behavior (IWB), as mediated by autonomous motivation and participative leadership moderation. The study was conducted on a sample of 246 employees from various public and private organizations, recruited through different social networks. The moderated mediation analysis provided evidence about the impact of employees’ PsyCap on their innovative behavior at work. This behavior will be higher when individual factors (PsyCap) and social factors (participative leadership) interact with one of the most self-determined forms of motivation. Our findings highlight the importance of the individual’s positive psychological capital in activating the resources and motivation, necessary to develop innovative behavior in employees, thus achieving organizational success in today’s dynamic and competitive business environment. The results also confirmed the moderating effect of participative leadership on the relationship between autonomous motivation and innovative behavior of employees, supporting that the relationship will be stronger when participative leadership is higher. Theoretical and practical implications are discussed, as well as limitations and suggestions for future studies.