Background: Home-based postnatal care after hospital discharge has become an integral part of postnatal care. This study aimed to determine the factors relating either to individuals or the healthcare system that affect enrollment and full participation (adherence) in the French home-based postnatal coordinated care program (PRADO). Methods: All admitted women for delivery in a French district over one year and eligible for this home-based midwifery support after hospital discharge were included (N = 4189). Both a simple probit model and a probit Heckman selection model were used. The control variables were the characteristics of the women, the municipalities, and the hospitals. Results: Approximately 68% of the eligible women chose to enroll in the PRADO program, of who nearly 60% fully participated in this program. Enrollment in the program was influenced mostly by the family context, such as the woman’s age at the time of her pregnancy and the number of children in the household, the woman’s level of prenatal education and information about postnatal care, as well as some hospital variables such as the characteristics and organization of the maternity units. Full participation in the program was influenced by the accessibility to health professionals, particularly midwives. Furthermore, the women’s level of prenatal education and information about postnatal care, as well as their accessibility to health professionals, correlated with the socioeconomic environment. Conclusion: While individual factors impacted enrollment in the PRADO program, only healthcare system-related factors influenced full participation in the program. A public health policy promoting home-based postnatal care could increase the women’s participation by improving their level of prenatal education and information about postnatal care. In addition, reducing regional inequality is likely to have a positive impact, as the availability of health professionals is a key factor for participation in home-based postnatal coordinated care.