["Journal of Organizational Behavior, EarlyView. ", "\nABSTRACT\nWork from home (WFH) is recognized as carrying both risks and benefits for individuals. However, its impact on romantic couples remains poorly understood. Drawing on boundary theory and family systems theory, we propose that WFH can render certain couples vulnerable to separation and trace the process through which this occurs. Specifically, when romantic partners hold incongruent preferences for segmenting work and home, or when both have a high preference for segmentation, WFH employees might experience heightened work‐to‐home conflict. This conflict drains resources needed for intimacy, fostering mutual loneliness and, ultimately, relationship dissolution deliberations. Across two longitudinal studies of dual‐earner couples in Germany (n = 170, n = 1561), we found nuanced support for this model. Dyadic response surface analyses showed that incongruent segmentation preferences affected the work‐to‐home conflict of employees in divergent ways—exacerbating it for some, mitigating it for others. As expected, a joint preference for segmentation was consistently associated with heightened work‐to‐home conflict in WFH employees. Work‐to‐home conflict was linked to loneliness in both partners, which explained dissolution deliberations. Overall, our research highlights that WFH is a work arrangement that has couple‐level consequences—beneficial for some, but a risk factor for others.\n"]