Indoor Residual Spraying (IRS), the use of insecticides inside residences for malaria control, may cause elevated exposure to insecticides such as dichlorodiphenyl trichloroethane (DDT). Evidence suggests that DDT exposure may increase blood pressure but no study has investigated associations with hypertensive disorders of pregnancy (HDP) in an IRS area. We measured the serum concentration of DDT and its breakdown product dichlorodiphenyl trichloroethylene (DDE) at the time of delivery among 733 rural South African women participating in the Venda Health Examination of Mothers, Babies and their Environment (VHEMBE). We also collected data on HDP diagnosis through questionnaires administered to participants and medical record abstraction. We used multiple logistic regression models to examine the relation between DDT/E and HDP. p,p′-DDT and p,p′-DDE serum concentrations were associated with HDP based on self-report (OR = 1.50; 95%CI = 1.10, 2.03 for p,p′-DDT and OR = 1.58; 95%CI = 1.09, 2.28 for p,p′-DDE) and medical records (OR = 1.32; 95%CI = 0.99, 1.75 for p,p′-DDT and OR = 1.47; 95%CI = 1.03, 2.09 for p,p′-DDE). p,p′-DDE was also associated with gestational hypertension (OR = 1.44; 95% CI = 1.00, 2.07). Exposure to DDT and DDE may be associated with elevated risks of HDP in South African women residing in an area sprayed for malaria control.