Objective: This study investigated whether pre-deployment dissociation was associated with previously identified post-traumatic stress disorder (PTSD) symptom trajectories from before to 2.5 years after military deployment. Furthermore, it examined whether the tendency to dissociate, pre-deployment personality factors, conceptualized by the Big Five model, and previous trauma represented independent risk factors for post-deployment PTSD symptoms.Method: This prospective study included the entire team of 743 soldiers from the Danish Contingent of the International Security Assistance Force 7 deployed to Afghanistan in 2009. Data consisted of self-report measures and were collected six times: before deployment; during deployment; and 1–3 weeks, 2 months, 7 months and 2.5 years after homecoming.Results: The findings indicate significant associations between pre-deployment dissociation and six PTSD trajectories (p < 0.001, η2 = 0.120). Based on mean differences in dissociation for the six trajectories, two main groups emerged: a group with high dissociation scores at pre-deployment, which had moderate PTSD symptom levels at pre-deployment and fluctuated over time; and a group with low dissociation scores at pre-deployment, which had low initial PTSD symptom levels and diverged over time. Our study also confirmed previous findings of a positive association between neuroticism and dissociation (r = 0.31, p < 0.001). This suggests that negative emotionality may be a vulnerability that enhances dissociative experiences, although a causal link cannot be concluded from the findings. Finally, pre-deployment dissociation, pre-deployment neuroticism and a history of traumatic events, as independent factors, were significant predictors of post-deployment PTSD (p < 0.001, R2 = 0.158).Conclusions: The study emphasizes the multiplicity of factors involved in the development of PTSD, and group differences in dissociative symptoms support the heterogeneity in PTSD. Further, this study points to specific aspects of personality that may be targeted in a clinical setting and in pre-deployment assessments in the military.