As a kind of cross-boundary behavior, work-related electronic communications during non-working time（WEC_NWT）included the conception of frequency and affective tone. With the data from 448 employees, the present research examined the differential effects of frequency and affective tone about the supervisor’s WEC_NWT, as well as the boundary influences of SSG and the employees’ work-home segmentation. The results indicated that WEC_NWT’s frequency had positive effects on the employees’ emotional exhaustion and turnover intention; while WEC_NWT’s positive affective tone showed negative influence on the emotional exhaustion and turnover intention. In addition, SSG had buffering effect on the relationship of WEC_NWT’s frequency on emotional exhaustion, and SSG could intensify the negative relation between positive affective tone and emotional exhaustion. Moreover, employees’ work-home segmentation could intensify the positive relationship of WEC_NWT’s frequency with emotional exhaustion and turnover intention. But employees’ work-home segmentation could attenuate partially the negative influence of WEC_NWT’s positive affective tone on emotional exhaustion.