Guided by Pekrun's (2006) control-value theory of achievement emotions, we investigated the mediating role of control and value appraisals in the relations between students' perceptions of teaching and their academic emotions. To account for the highly fluctuating and dynamic nature of emotions, we used the experience sampling method complemented by within-person mediation analyses. In 2 studies, n = 122 (Study 1) and n = 149 (Study 2) high school students reported on their real-time perceptions of teaching characteristics (grouped into two second-order factors: supportive presentation style and excessive lesson demands), their control and value (intrinsic and extrinsic) appraisals, and their academic emotions of enjoyment, anxiety, and boredom (n = 1,520/2,669 assessments within students). Across the 2 studies, we found consistent results on the intraindividual level that are in line with an assumption of the control-value theory: Appraisals of control and value mediated the effects of perceived characteristics of teaching on academic emotions (e.g., supportive presentation style showed positive effects on control, which, in turn, showed positive effects on enjoyment). At the same time--and contributing to further developments of the control-value theory--the relative importance of direct and indirect effects (i.e., amount of mediation) differed across emotions. For example, there was a strong direct effect of supportive presentation style on enjoyment, but no effect on anxiety. Similarly, appraisals differed in their relative importance as mediators both within and across emotions (e.g., extrinsic value was mainly relevant for anxiety, whereas intrinsic value contributed to enjoyment and boredom).