Background: Since scholastic well-being is connected with intrinsic motivation, positive emotions and effective learning, it is highly relevant for educational research. It is influenced by a variety of individual and contextual determinants and differs for several groups of students with respect to their environmental conditions. Aims: Up to now, there has been neither approach in answering questions about group-differences between students with high or low levels of scholastic well-being nor in defining variables that are most different for these groups. The current study addresses this research gap by investigating differences in familial and scholastic aspects in two distinct groups of students (extreme high or low level of scholastic well-being). Sample and Method: Self-report questionnaires from N = 852 fifth graders were evaluated using the multivariate analysis of variance (MANOVA) and a discriminant analysis. Results: Results of the discriminant analysis show that attainment of academic educational track, good classroom-management, positive social climate in class and high clarity of instruction, as well as low parental pressure on performance are characteristics that classify students with an extreme high level of scholastic well-being. Therefore, those variables can be used to divide students into disjoint groups without having any information about their actual scholastic well-being. Conclusion: Firstly, it can be deduced from the findings that measures within the schools to promote scholastic well-being should start with the improvement of instructional quality and social climate. Second, reduction of parental pressure on performance as well as the implementation of successful cooperation between families and schools is vital.