Intraindividual differences in executive functions (EFs) have been rarely investigated. In this study, we addressed the question of whether the emotional fluctuations that schoolchildren experience in their classroom settings could generate substantial intraindividual differences in their EFs and, more specifically, in the fundamental unifying component of EFs, their inhibition function. We designed an experimental research with ecological validity within the school setting where schoolchildren of three age groups (8-, 10-, and 12-year-olds) were involved. We executed three experiments. In Experiment 1, using a between-participants design, we isolated a classroom episode that, compared with the other episodes, generated significant differences in inhibitory function in a consequent Go/NoGo task. This was an episode that induced frustration after the experience of anxiety due to the uncertainty. Experiment 2, using a within-participants design, confirmed both the induced emotions from the episode and the intraindividual variability in schoolchildren’s inhibition accuracy in the consequent Go/NoGo task. Experiment 3, again using a within-participants design, examined whether the same episode could generate intraindividual differences in a more demanding inhibition task, namely the anti-saccade task. The experiment confirmed the previous evidence; the episode generated high variability that in some age groups accounted for more than 1.5 standard deviations from the interindividual variability between the schoolchildren of the same age. Results showed that, regardless of their sex and the developmental progression in their inhibition with age, the variability induced within participants from the experienced frustration was very high compared with the interindividual variability of the same age group.