In this study, we used a within‐person daily research paradigm to examine the relationship between daily family–work conflict (FWC) and daily job performance. On the basis of theory on dynamic behavior, we hypothesized that concentration serves as a mechanism through which daily FWC impairs daily job performance. We further predicted that psychological detachment from work during time‐off (i.e., mentally switching off) buffers the negative relationship between daily FWC and daily job performance. Ninety‐five employees completed daily surveys over one workweek. Multilevel modeling results showed that daily FWC was negatively associated with daily job performance and that concentration mediated this relationship. Furthermore, general psychological detachment, but not daily psychological detachment, buffered the negative relationship between daily FWC and daily job performance. The current findings suggest that daily FWC has negative performance implications and that the general level rather than the daily level of psychological detachment from work helps alleviate the negative implications. Copyright © 2013 John Wiley & Sons, Ltd.