The new world of work has seen many employees adapting to the dynamics of working from home. With the change in location, the factors that promote employee thriving while working have altered as well. Drawing on the literature on thriving and broaden-and-build theory, this research examines how family-work affect helps employee thriving through increased exploration, with conditional effect of ambidextrous leader. Based on two studies (n = 483), results confirm the proposed model. In Study 1, the mediating effect of exploration in the relationship between family-work affect and thriving is supported on a sample of university students. Study 2 corroborates the mediating effect and supports the moderating role of ambidextrous leadership among employees. Specifically, the positive effects of family affective experiences on an individual’s exploration were greater under high levels of ambidextrous leadership behaviors. The practical recommendations offered are intended to increase thriving while working from home.