Early academic adjustment has been found to be predictive of later academic success. This study sought to determine how child emotionality at school, specifically positive and negative emotions, as well as the quality of the school, might affect child's academic achievement. Further, the possibility that emotionality and school quality interact was tested. Two hundred and twenty eight second grade children's expressions of positive and negative emotions were observed in the school setting. Teachers also submitted questionnaires on the children's positive emotionality. Academic adjustment was measured by standardized tests and teacher reports. School quality scores were based on multiple indicators obtained from online public information data. Regression analyses and multi-level modeling (when necessary) were used to predict academic performance from children's emotions, school quality, and their interaction. Results demonstrated that school quality was at least marginally positively related to all aspects of children's academic competence. Further, teacher-reported positive emotion positively predicted all scores of academic competence, and teacher-reported dispositional positive emotion positively predicted Woodcock Johnson III applied problems subtest scores. Further, interaction effects showed that teacher-reported positive emotion and school quality significantly predicted teacher-reported academic competence and Woodcock Johnson III applied problems subtest scores. Using both statistical strategies (MLM & regressions), observer-reported positive emotion and school quality marginally significantly predicted Woodcock Jonson III applied problems subtest scores. The results indicate that children's emotional behaviors at school, as well as school quality, play a role in the development of children's academic achievement.