Background: Although breastfeeding is one of the top priorities for public health in China, the rate of breastfeeding is still low and a large number of women do not initiate breastfeeding due to various reasons. Hence, this study aimed to understand the decision-making of non-initiation and reveal the underlying reasons in order to protect, support, and promote breastfeeding. Methods: In-depth, exploratory interviews were carried out with 13 new mothers who did not initiate breastfeeding. The collected data were analyzed by inductive content analysis. Results: Although mothers generally understood the protective effects of breastfeeding, they believed that formula milk is a good alternative to human milk and even better in some aspects. Five core themes related to non-initiation decision-making emerged: (1) expected breastfeeding stress; (2) maladjustment to the maternal role; (3) concerns about physiological issues; (4) the lack of knowledge about the risks of artificial feeding; (5) belief that it is better not to initiate than to interrupt. Conclusions: The environment for mothers to breastfeed in China is not supportive enough, and the medical staff and families should be held responsible for the non-initiation of breastfeeding. More professionals are needed to support mothers to solve their problems and breastfeeding education should be further expanded.