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Background Gestational syphilis requires early detection and proper treatment to prevent negative maternal-fetal outcomes. This study aimed to evaluate the effectiveness of an educational intervention on treatment adherence and knowledge about syphilis in postpartum women with positive Treponema pallidum results. Methods A randomized, parallel, and open clinical trial was conducted with 64 postpartum women who tested positive for T. pallidum, assigned to two groups (1:1 ratio). The Intervention Group (IG) received an educational intervention on syphilis, including an explanatory leaflet and hands-on demonstrations, along with standard guidelines. The Control Group (CG) received standard guidelines alone. Pre-test and post-test assessments were conducted to measure knowledge and treatment adherence. Statistical analyses included descriptive and inferential methods, assessing group homogeneity using the Chi-square or Fishers exact test. The interventions effectiveness was determined using relative risk, and pre- and post-test scores were compared using the independent t test. Results The post-test revealed improvements in knowledge scores for general knowledge, treatment, and prevention domains ( p < .05). The IG demonstrated an increase in post-test knowledge scores ( p = .001), with association between post-test scores and treatment adherence ( p = .001). Conclusion The educational intervention on syphilis improved knowledge and treatment adherence in postpartum women with syphilis.