Affect is a critical factor impacting students' goal setting and goal achievement in learning. While existing studies have demonstrated the vital role of affect in learning and goal achievement, the day-to-day fluctuations of affect and their impact on learning have rarely been examined. This study explored the dynamic relationships between positive affect (PA), negative affect (NA), and daily learning goal achievement (LGA) in 72 college students ahead of a high-stakes test, analyzing 32 days of survey responses totaling 2111 observations. We employed dynamic structural equation modeling (DSEM) to assess the stability, variability, and potential reciprocal relationships of PA, NA, and LGA. Additionally, we investigated the effects of depression, age, and the number of semesters studied on these variables. Results indicated that PA, NA, and LGA remained stable over the observation period, with no systematic changes or trajectories, yet exhibited significant fluctuations within and between participants. All autoregressive effects for PA, NA, and LGA were significant. Both PA and NA were significantly related to concurrent measures of LGA, although no significant cross-lagged relationships between PA and NA were found. Variability in PA, NA, and LGA was significantly explained by students' age, number of semesters studied, and level of depressive symptoms. Further findings and implications of the study are discussed.