For working students, reconciling work and school lives is a major challenge. Emerging ubiquitous information and communication technologies (ICTs) further exacerbate this challenge, as a constant connection to work via ICTs blurring the boundaries between work and school domains. While the influence of ICTs on users’ work and personal lives has received considerable research attention, the lens has not focused on how ICTs usage affect working students. In this study, we theorized the process by which working students’ ICTs usage during school time affects their work-school interface experiences. We conducted a time-lagged design with two-phase data collection, and a sample consisted of 266 working students was used to test the proposed hypotheses and theoretical model. The results suggest that as the frequency of work-related ICTs usage during school time increases, working students will experience more work-school conflict; the elevated experience of work-school conflict in turn negatively affects working students’ work-school balance satisfaction. Furthermore, our results indicate that the negative effects of ICTs usage presented in this study are stronger (weaker) for those with high segmentation (integration) preference. These findings add to our understanding of the consequences of ICTs usage regarding working students’ work-school interface. We provide some recommendations on how to minimize work-school conflict caused by ICTs usage and enhance balance satisfaction, and provide directions for future research in this topic.