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Grounded in Situated Expectancy-Value Theory, this study used experience sampling to explore the relationships among motivation, multitasking behaviors, and engagement among university students. Multilevel structural equation modeling revealed that motivation plays a central role in shaping engagement, while multitasking appears to hinder students’ ability to fully engage with the task. In addition, multitasking operates through different mediating mechanisms at the within- and between-person levels. Momentary increases in importance and intrinsic value reduced multitasking, which in turn promoted more positive emotions, effort, and concentration. At the between-person level, students perceiving higher cost than peers were more likely to multitask, which in turn lowered their concentration. These findings offer practical implications for enhancing students’ motivation to discourage multitasking and promote engagement.