Adherence to nonoccupational post-exposure prophylaxis (nPEP) among sexual violence (SV) victims and their retention in care after SV represent significant challenges. This study aimed at identifying predictors of adherence to nPEP and retention in clinical-laboratory follow-up among SV victims in São Paulo, Brazil. We conducted a retrospective cohort study of SV victims admitted to care and follow-up at the SV unit of the main reference hospital in São Paulo within 72 h following the SV episode. Eligible patients were submitted to a standardized protocol that included nPEP, screening, and management for other sexually transmitted infection as well as emergency contraception. Predictors of adherence to nPEP for 28 days and retention in care until discharge at 180 days after admission were analyzed. A total of 199 SV episodes in 197 victims were recorded from January 2001 to December 2013 (156 months). Of those episodes, 167 were eligible to receive nPEP and 160 (96%) actually received a prescription. Overall 104/160 [65%, 95% confidence interval (CI) 57-72] SV victims, who received nPEP, were fully adherent to nPEP up to 28 days, whereas 89/199 (45%, 95% CI 38-52) were retained in care for 180 days following admission. In multi-variate analysis, patients undergoing at least one psychological consultation (n = 126) were more likely to adhere to nPEP [adjusted odds ratio (adjOR) 8.32; 95% CI 3.0-23.3] and be retained in care for 6 months (adjOR 40.33; 95% CI 8.33-195.30) compared to patients not receiving psychological support. In contrast, study outcomes were not associated with victims' age and sex and with type of perpetrator. In our cohort, provision of psychological care was shown to be associated with enhanced adherence to nPEP and retention in care.