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Innovative behavior is a microfoundation of an organization’s innovation. Knowledge workers are the main creators of innovations. With the boundaries between work and family becoming increasingly ambiguous, the purpose of this study is to explore how the work–family conflict affects knowledge workers’ innovative behavior and when such a conflict arises.

To test the theoretical model, this study collected data from a time-lagged matched sample of 214 dual-career couples. The data were analyzed with the bias-corrected bootstrapping method.

The results of this study showed that work-to-family conflict had not only a direct negative effect on knowledge workers’ innovative behavior but also an indirect effect through spouses’ within-family emotional exhaustion and knowledge workers’ family-to-work conflict. If wives’ gender role perceptions are traditional, then the indirect serial mediating effect is weakened, but if such perceptions are egalitarian, then the mentioned effect is aggravated.

In terms of organizational implications, managers could alter their approach by reducing detrimental factors such as work–family conflict to improve knowledge workers’ innovative behavior. Emotional assistance programs for both knowledge workers and their spouses can be used to prevent the detrimental effect of work–family conflict on innovative behavior. As to social implications, placing dual-career couples into a community of likeminded individuals and promoting their agreement on gender role identity will greatly reduce the negative effects of work–family conflict.

Starting from the perspective of the behavior outcome of knowledge management, this study advances the existing knowledge management literature by enriching the antecedents of knowledge workers’ innovative behavior, illuminating a spillover–crossover–spillover effect of work–family conflict on knowledge workers’ innovative behavior and identifying the boundary condition of this transmission process.