Background: Postpartum preeclampsia has been implicated in increasing hospital re-admissions, maternal morbidity, and mortality worldwide. The knowledge of the risk factors of postpartum preeclampsia would be helpful in formulating strategies to aid in the prevention, early diagnosis, and timely treatment of this disorder. Thus, this study aimed to identify the risk factors associated with the development of new-onset postpartum preeclampsia and persistent postpartum preeclampsia in the Ghanaian setting. Methods: This case–control study was conducted at the Obstetrics and Gynecology units of Komfo Anokye Teaching Hospital and the Kumasi Regional Hospital, both located in the Ashanti Region of Ghana. A total of 65 postpartum preeclamptic women (33 new-onset postpartum preeclampsia and 32 persistent postpartum preeclampsia) and 65 normotensive postpartum mothers were recruited from 48 h to 6 weeks post-delivery. Questionnaires were administered to assess the socio-demographic, lifestyle, obstetric characteristics, and past medical history of the study participants. Results: Physical inactivity ( p < 0.0001), infrequent antenatal visits ( p < 0.0001), analgesic use ( p < 0.0001), and cesarean delivery ( p = 0.021) were significantly associated with both the new-onset postpartum preeclampsia and persistent postpartum preeclampsia. Contraceptive use was significantly associated with the development of new-onset postpartum preeclampsia ( p < 0.0001) while women with low-birthweight babies are also at high risk of developing persistent postpartum preeclampsia ( p < 0.0001). Conclusion: Physical inactivity, infrequent antenatal visits, analgesic use, contraceptive use, and cesarean delivery are major predisposing risk factors for the development of postpartum preeclampsia. Screening using these risk factors, close monitoring and follow-up observation of women after delivery would be beneficial in identifying and managing postpartum preeclampsia.