Value orientations are believed to influence learning in school. We assume that this influence is mediated by the valences attached to specific school subjects. In a questionnaire study (704 students from 36 classes) achievement and well-being value orientations were measured. Students also rated valence scales for the school subjects German and Mathematics and reported their respective grades. In order to take into consideration the nested data structure, the mediation hypotheses were tested using the Hierarchical Linear Model in a series of intercept only models. School grades were significantly predicted by value orientation. A mediation analysis indicated that this relation was completely mediated by the valences of the different school subjects. Descriptions of students representing value prototypes are appended. (Contains 4 figures, 2 tables, and 3 notes.)