Building on Affective Events Theory (AET), this study examined within-person relationships between employee perceptions of day-level leader-member exchange (LMX) and day-level positive affect as well as between positive affect and recovery from work in the evening (i.e., relaxation, mastery, control, and psychological detachment from work). In addition, LMX variability was examined as a moderator of these within-person relationships. Employees (N = 160) completed surveys at the end of the workday and in the evening across five consecutive workdays. Results indicate direct relationships between perceptions of LMX and employee positive affect at work. In addition, positive affect was positively associated with two of the four recovery experiences (mastery and relaxation). Furthermore, LMX variability across the workweek moderated these positive indirect effects such that the indirect associations between the perceptions of LMX and employees’ recovery experiences during the evening via positive affect was only positive when LMX variability was low. The indirect effects, however, were nonsignificant when LMX variability was moderate or high. The present study expands LMX research by adopting a dynamic within-person perspective and by connecting the literature on workplace leadership with the literature on recovery from work, indicating that perceptions of LMX can potentially impact employees’ nonwork time.