Values are connected to how a person perceives the environment and themselves. One can talk about a certain dynamic of values over time. Changes in the importance of values occur due to existing situations in the external environment or to a significant alteration in one’s internal motivation. The goals of our research were to determine the value structure of preadolescents at risk of school dropout and to identify differences in values depending on the type of vulnerability, gender and geographical region. A total of 120 pre-teens (64 boys and 56 girls) at risk of school dropout participated in the study. We used the Values Questionnaire, part of the PEDb computerised platform (created by Cognitrom), which is calibrated for the Romanian population. The results have revealed that the most important values for pre-teens at risk of school dropout are related to social relations, skill development, free time and compliance with the rules. Significant differences were highlighted between boys and girls, respectively between socially assisted students and those with an absent parent, considering the value structure. Also, through a single-factor multivariate analysis of variance, important differences were noted in terms of free time and social relations, depending on the geographical region. The study findings are valuable resources for teachers (who can positively influence the social and educational integration of preadolescents by using student-centered learning and taking into account their value system), parents, and researchers eager to better understand the value structure of students at risk of school dropout.