Research based in the United States, with its relatively open educational system, has found that personality mediates the relationship between parents’ and child’s educational attainment and this mediational pattern is especially beneficial to students from less-educated households. Yet in highly structured, competitive educational systems, personality characteristics may not predict attainment or may be more or less consequential at different points in the educational career. We examine the salience of personality in the educational attainment process in the German educational system. Data come from a longitudinal sample of 682 17 to 25 year-olds (54% female) from the 2005 and 2015 German Socio-Economic Panel (SOEP). Results show that adolescent personality traits—openness, neuroticism, and conscientiousness—are associated with educational attainment, but personality plays a negligible role in the intergenerational transmission of education. Personality is influential before the decision about the type of secondary degree that a student will pursue (during adolescence). After that turning point, when students have entered different pathways through the system, personality is less salient. Cross-national comparisons in a life course framework broaden the scope of current research on non-cognitive skills and processes of socioeconomic attainment, alerting the analyst to the importance of both institutional structures and the changing importance of these skills at different points in the life course.