The use of Internet tools virtually increases the work connectivity behavior after-hours (WCBA), is becoming increasingly common. Previous studies have found that WCBA has a double-edged sword effect on turnover intention (TI), but the configuration effect had been ignored. To investigate the configuration effect of WCBA, internal factors (i.e., psychological capital and mindfulness), and external factors (i.e., family-to-work conflict and social support), on TI. A total of 305 participants have been collected using convenience sampling. A questionnaire that covers six personal and contextual scales of the WCBA, psychological capital (PsyCap), mindfulness, family-to-work conflict (FWC), social support (SS), and TI, was used to gather data. Adhering to configurational theory, the study was conducted using fuzzy-set qualitative comparative analysis (fsQCA). it was revealed that seven antecedent configurations could achieve high TI, among them, WCBA existed in S4 and S6 but was absent in S5 and S7. Moreover, WCBA can exist and be absent in S1-S3 simultaneously; and for the 13 configurations that achieve low level of TI, WCBA can exist or not. Therefore, although the achievement of low level of TI is to some extent influenced by WCBA, it relies more on the influence of other factors (i.e., PsyCap, mindfulness, ∼ FWC, and SS). The study proves that WCBA has a double-edged effect on TI. The absence of FWC and existence of SS, PsyCap, and mindfulness are critical variables to buffer the loss of psychological resources caused by WCBA and recover psychological resources in time. These results may be helpful to recognize the negative effect of WCBA existence, accompanied with the absence of mindfulness on TI; also, the absence of SS was as crucial as the existence of FWC in the process of achieving high level of TI.