Recent evidence has shown that a significant portion of the variance in work-family conflict (WFC) and work-family enrichment (WFE) can be attributed to the within-person level on a daily basis. However, we still need to know how leaders influence employees’ daily fluctuations in WFC and WFE. Drawing on the work-home resources model and behavioral plasticity theory, this study attempts to explore the cross-level effects of leader–member exchange (LMX) on employees’ daily WFC and WFE and the extent to which such cross-level effects are moderated by employees’ parental role commitment (PRC) and marital role commitment (MRC). Using ESM data from 80 full-time and married employees across 15 consecutive days, we found that LMX was positively related to daily WFE but was not significantly related to daily WFC. Furthermore, MRC moderated the relationship between LMX and daily WFC such that the relationship was negative and significant only for employees with low MRC. PRC moderated the relationship between LMX and daily WFE such that the relationship was positive and significant only for employees with low PRC. The contributions and implications of these findings are discussed.