Students’ competence beliefs and task values are proximal psychological predictors of their achievement-related choices and academic achievement. Situated expectancy-value theory (SEVT) suggests that these beliefs are situationally sensitive and interact over short periods of time. In the present study, we explored the dynamic nature of students’ situation-specific expectancy-value beliefs in five sections of an introductory calculus course across one semester (11 weeks, N = 429). Using psychometric network analysis, we examined how facets of the SEVT framework are related between persons (i.e., between-person network), within situations (i.e., within-person contemporaneous network), and from one time point to the next across one semester (i.e., within-person temporal network). Results suggested that differences existed among motivational constructs across the three networks in that costs and positively-valenced facets of motivation (i.e., competence and values) were relatively independent of each other within a given situation, but showed some significant cross-lagged effects over time. Our results suggest that interventions to support students in STEM should target positively and negatively valenced constructs (i.e., values and costs).