Mother and newborn skin-to-skin contact (SSC) after birth has numerous protective effects. Although positive associations between SSC and breastfeeding behavior have been reported, the evidence for such associations between early SSC and breastfeeding success was limited in high-income countries. This quasi-experimental intervention design study aimed to evaluate the impact of different SSC regimens on newborn breastfeeding outcomes in Taiwan. In total, 104 healthy mother–infant dyads (52 in the intervention group and 52 in the control group) with normal vaginal delivery were enrolled from 1 January to 30 July 2019. The intervention group received 60 min of immediate SSC, whereas the control group received routine care (early SSC with 20 min duration). Breastfeeding performance was evaluated by the IBFAT and BSES-Short Form. Generalized estimating equations (GEEs) were used to evaluate the effectiveness of the intervention. In the intervention group, the breastfeeding ability of newborns increased significantly after 5 min of SSC and after SSC. The intervention also improved the total score for breastfeeding self-efficacy (0.18 point; p = 0.003). GEE analysis revealed that the interaction between group and time was significant (0.65 point; p = 0.003). An initial immediate SSC regimen of 60 min can significantly improve neonatal breastfeeding ability and maternal breastfeeding self-efficacy in the short term after birth.