A daily diary and two experience sampling studies were carried out to investigate curvilinearity of the within-person relationship between state neuroticism and task performance, as well as the moderating effects of within-person variation in momentary job demands (i.e., work pressure and task complexity). In one, results showed that under high work pressure, the state neuroticism-task performance relationship was best described by an exponentially decreasing curve, whereas an inverted U-shaped curve was found for tasks low in work pressure, while in another study, a similar trend was visible for task complexity. In the final study, the state neuroticism-momentary task performance relationship was a linear one, and this relationship was moderated by momentary task complexity. Together, results from all three studies showed that it is important to take into account the moderating effects of momentary job demands because within-person variation in job demands affects the way in which state neuroticism relates to momentary levels of task performance. Specifically, we found that experiencing low levels of state neuroticism may be most beneficial in high demanding tasks, whereas more moderate levels of state neuroticism are optimal under low momentary job demands.