In the last few decades, academic circles have paid extensive attention to the psychological state of employees (e.g., thriving at work), but only a few scholars have inspected this phenomenon among professional women. For professional women, the family is as important as work. Therefore, the attitude from family members, especially the spouses in this regard (e.g., benevolent sexism) may have a significant impact on the working state and performance of professional women. Previous studies examined the antecedents of thriving at work but they concentrated on work characteristics such as colleagues’ interaction with each other, contextual characteristics, and work resources. However, the family plays a crucial role in the life of professional women, and antecedents of family origin may affect thriving at work of professional women. Based on the work-family resource model, this article constructed a moderated mediation model to verify the cross-domain influence of spouses’ benevolent sexism on professional women’s thriving at work, and further studied the mediating role of family-work conflict and the moderating role of work centrality were further investigated. The study collected data from dual-employee couples in shanghai and Zhejiang province through electronic questionnaires, and finally recovered 208 valid questionnaires. To reduce the errors of homology, this study procedurally collected questionnaires in the form of couples pairing, and used the Harman's univariate analysis for common method bias testing and Mplus for confirmatory factor analysis. The results confirmed that the study was not affected heavily by the errors of homology. The results indicated that spouses’ benevolent sexism was negatively related to thriving at work, such relationship was partially mediated by family-work conflict, and finally, work centrality moderated the relationship between spouses’ benevolent sexism and thriving at work in such a way that the relationship was significant when work centrality was low. The findings provide novel theoretical and practical signification. First, the study is unique in a way that it expands the antecedents of thriving at work particularly in the family domain. Second, it takes the professional women as a research object which enriches the research on the family-work relationship of professional women. Third, by exploring the moderating role of work centrality, it provides a relatively comprehensive view that reducing benevolent sexism by spouses is more likely to help working women to increase their thriving at work. In addition to the theoretical contributions highlighted above, this study also put forward some practical suggestions to enterprises and families. For instance, spouses should help women with housework. Organizations should actively help them to coordinate family-work relationship, improve working conditions, and enhance performance. Moreover, under the influence of work centrality, professional women's work and family life may show a trend of integration which requires professional women to make efforts to create a balance. Lastly, it is suggested that future studies may further explore the other possible effects of family-friendly gender discrimination on professional women.