ABSTRACT: Background: Emergency cesarean section (EMCS) and breastfeeding difficulties increase the risk of postpartum depressive (PPD) symptoms. Early initiation of breastfeeding (EIBF) may not only alleviate PPD symptoms but also facilitate subsequent breastfeeding success. EMCS is a risk factor for not practicing EIBF. Therefore, it is important to understand the relationship between EMCS, EIBF, and PPD symptoms. Methods: We conducted a prospective cohort study in three areas of China. At baseline, a total of 965 mothers completed electronic questionnaires within 72 h postpartum. Women were screened for PPD symptoms using the Edinburgh Postpartum Depression Scale (EPDS). Multivariate logistic regression was used to identify the determinants of PPD symptoms. Mediation analysis was used to determine if EIBF mediated the relationship between delivery mode or breastfeeding education source and PPD symptoms. Results: The prevalence of EIBF was 40.6%; 14% of 965 mothers experienced EMCS, and 20.4% had PPD symptoms. The risk factors for developing PPD symptoms were excessive gestational weight gain (adjusted odds ratio [aOR] = 1.55, confidence interval [95% CI]: 1.03–2.33, p = 0.037) and EMCS (aOR = 2.05, 95% CI: 1.30–3.25, p = 0.002). The protective factors for developing PPD symptoms were monthly household income over CNY 10000 (aOR = 0.68, 95% CI: 0.47–0.97, p = 0.034), EIBF (aOR = 0.49, 95% CI: 0.34–0.72, p < 0.001), and prenatal breastfeeding education from nurses (aOR = 0.46, 95% CI: 0.29–0.73, p = 0.001). EIBF indirectly affected PPD symptoms in patients who had undergone EMCS (percentage mediated [PM] = 16.69, 95% CI: 7.85–25.25, p < 0.001). The source of breastfeeding education through EIBF also affected PPD symptoms (PM = 17.29, 95% CI: 3.80–30.78, p = 0.012). Conclusion: The association between EMCS on PPD symptoms was mediated by EIBF. By providing breastfeeding education, nurses could also help alleviate PPD symptoms.