Improving maternal health is one of the Sustainable Development Goals. Hospital service areas (HSAs), which contain most hospitalization behaviors at the local scale, are crucial for health care planning. However, little attention has been given to HSAs for maternal care and the hierarchy structure. Considering Hubei, central China, as a case study, this study aims to fill these gaps by developing a method for delineating hierarchical HSAs for maternal care using a network optimization approach. The approach is driven by actual patient flow data and has an explicit objective to maximize the modularity. It also establishes the hierarchical structure of maternal care HSAs, which is fundamental for the planning of hierarchical maternal care and referral systems. In our case study, 45 secondary HSAs and 22 tertiary HSAs are delineated to achieve maximal modularity. The HSAs perform well in terms of indices such as the Localization Index and Market Share Index. Furthermore, there is a complementary relationship between secondary and tertiary hospitals, which suggests the need for referral system planning. This study can provide evidence for the validity of the HSA and the planning of maternal care HSAs in China. It also provides transferable methods for planning hierarchical HSAs in other developing countries.