In a society where employees increasingly use mobile devices to execute work actions, the emotive domain accompanying these actions is crucial in further understanding the potential issues of the engagement with mobile devices for decision making, employees’ work performance and work activities management. Yet, to date, there is a dearth of research in how emotions emerge and impact people’s usage of mobile devices for work-related activities. We address this gap by exploring, through a qualitative study, the significances of the emotive domain emerging from the relations of users, their mobile devices, and the situations in which these interactions occur. We find that positive but predominantly negative emotions emerge through the relation of mobile devices and persons, and identify five spatiotemporal situations in which emotions emerge, resulting in three modalities of mobile devices-humans engagement. We provide researchers with a theoretical model for the analysis of emotions in relation to mobile device usage, and practitioners with suggestions on how managing mobile devices-employees interactions can be best addressed.