Background: Maximising women's participation and ensuring optimal outcomes will require that the women's perception barriers to postnatal prevention of Mother-to-Child Transmission (PMTCT) programme of HIV be addressed. However, little is known about women's perception barriers to postnatal PMTCT programme of HIV and how these barriers affect the women's health seeking behavior and uptake. Objective: This study sought to explore the women's perception barriers to postnatal PMTCT programme at a Johannesburg Community Health Centre during April-May, 2016. Methods: A qualitative study on 30 women (aged 20-39 years) was conducted at a Johannesburg community health (CHC), South Africa, during May-June 2016, after obtaining their consent. The data was analysed thematically to understand women's perception barriers to postnatal PMTCT programme. Results: The study found that inadequate counselling was perceived to be the single key health service barrier to PMTCT programme. At the individual level, adherence to ART was considered the leading women's barriers to the postnatal PMTCT. Exclusive breastfeeding was, however, perceived as important women's barriers to the postnatal PMTCT. Inadequate emotional support from families and community was a noteworthy women's perception barrier to the programme. Conclusion: The study makes two recommendations: firstly, the staff, programme managers and health policy makers need to be aware of the women's perception barriers to the postnatal PMTCT programme. Secondly, the programme should be strengthened by addressing perception barriers to the programme to enhance women participation to ensure optimal outcomes for women and their infants.