Research on school Psychological Capital (PsyCap) and achievement emotions have been carried out in parallel with almost no intersection. This study aims to explore the potential synergies between these two paradigms by investigating whether school PsyCap has a predictive effect on discrete achievement emotions. Chinese secondary school students (N = 1067) took part in the study. Structural Equation Modeling analyses were conducted to examine the linkage between these two variables after controlling for demographic variables of gender and year level, and crucial antecedents of parental expectations, the teacher-student relationship, and prior academic achievement. Results indicated that individual variation in school PsyCap was the significant predictor of achievement emotions. Specifically, school PsyCap was positively correlated with positive achievement emotions such as enjoyment, hope, and pride, while it was negatively correlated with negative achievement emotions such as anger, anxiety, shame, boredom, and hopelessness. Both limitations and implications are discussed.