Personality is known to be a key predictor for several aspects of close relationship functioning. Most likely, the influence of this psychological factor is even growing in contemporary societies, where the individual life biography is increasingly the result of personal preferences and less influenced by normative expectations and cultural institutions. In an era of high relationship instability, more and more people engage in a second union. Although it becomes increasingly relevant to study the effects of personality on close relationship functioning in higher order unions, this remained understudied until now. This study examines the impact of personality on partnership trajectories following divorce. First, we construct a typology of eight partnership trajectories, capturing the occurrence, order, and timing of different partnership events (e.g., repartnering, cohabiting, getting married) in the first 7 years after separation. Then, we use multinomial logistic regression to examine the association between personality and the post-separation partnership trajectories, thereby controlling for sociodemographic variables. The analyses are based on data from a large-scale representative survey, the Divorce in Flanders Survey. Results show that personality and sociodemographic factors are both important determinants for explaining post-separation partnership trajectories. Extraversion tends to increase the likelihood and speed of repartnering. Neuroticism lowers the stability in partnerships. Conscientiousness is related with a higher likelihood to remarry. A higher age at separation and the presence of children at home decrease the likelihood to repartner, while education increases this. The present study delivers an important contribution for unraveling part of the complex association between personality and partner relationship dynamics.