Postpartum care (PPC) has remained relatively neglected in many interventions designed to improve maternal and neonatal health in sub-Saharan Africa. The Missed Opportunities in Maternal and Infant Health project developed and implemented a context-specific package of health system strengthening and demand generation in four African countries, aiming to improve access and quality of PPC. A realist evaluation was conducted to enable nuanced understanding of the influence of different contextual factors on both the implementation and impacts of the interventions. Mixed methods were used to collect data and test hypothesised context–mechanism–outcome configurations: 16 case studies (including interviews, observations, monitoring data on key healthcare processes and outcomes), monitoring data for all study health facilities and communities, document analysis and participatory evaluation workshops. After evaluation in individual countries, a cross-country analysis was conducted that led to the development of four middle-range theories. Community health workers (CHWs) were key assets in shifting demand for PPC by ‘bridging’ communities and facilities. Because they were chosen from the community they served, they gained trust from the community and an intrinsic sense of responsibility. Furthermore, if a critical mass of women seek postpartum healthcare as a result of the CHWs bridging function, a ‘buzz’ for change is created, leading eventually to the acceptability and perceived value of attending for PPC that outweighs the costs of attending the health facility. On the supply side, rigid vertical hierarchies and defined roles for health facility workers (HFWs) impede integration of maternal and infant health services. Additionally, HFWs fear being judged negatively which overrides the self-efficacy that could potentially be gained from PPC training. Instead the main driver of HFWs’ motivation to provide comprehensive PPC is dependent on accountability systems for delivering PPC created by other programmes. The realist evaluation offers insights into some of the contextual factors that can be pivotal in enabling the community-level and service-level interventions to be effective.