Objective To explore the prophylactic effect of ergometrine maleate combined with calcium gluconate on postpartum hemorrhage in women with scarred uterus undergoing vaginal delivery. Methods A total of 115 puerpera with scarred uterus undergoing vaginal delivery were selected as the research subjects, and they were assigned to control group (58 cases) or observation group (57 cases) according to the random number table method. Both groups received oxytocin for treatment, based on which the control group received calcium gluconate for treatment, whereas the observation group received ergometrine maleate combined with calcium gluconate for treatment. The postpartum hemorrhage, coagulation function indices with respect to fibrinogen (FIB), activated partial thromboplastin time (APTT), thrombin time (TT), prothrombin time (PT), and hemoglobin level, red blood cell counts (RBC), serum Ca2+ concentration, hemodynamic indices in terms of mean arterial pressure (MAP), heart rate, as well as the occurrence states of adverse reactions were compared between puerpera of the two groups. Results The observation group exhibited a lower rate of postpartum hemorrhage as compared with the control group (P<0.05). The blooding volumes of the observation group within 2, 12, and 24 hours after delivery were less than those of the control group (P<0.05). After intervention, puerpera of both groups obtained decreased levels of FIB, hemoglobin, and a decreased RBC as compared with before intervention, but the observation group interpreted higher indices as above as compared with the control group (P<0.05); moreover, both groups depicted longer APTT, TT, and PT, and elevated MAP and heart rate as compared with before intervention, but the observation group demonstrated shorter or lower indices as above as compared with the control group (P<0.05), whereas the concentration of serum Ca2+ of both groups was elevated as compared with before intervention, and the observation group was higher than the control group (P<0.05). There was no statistically significant difference in the total incidence rate of adverse reactions between puerpera of both groups (P>0.05). Conclusion Employing ergometrine maleate combined with calcium gluconate for the treatment of puerpera with scarred uterus after vaginal delivery can effectively prevent postpartum hemorrhage, decrease postpartum hemorrhage rate, ameliorate coagulation function and hemodynamic levels, exerting a higher medication safety.