Human neonates can discriminate phonemes, but the neural mechanism underlying this ability is poorly understood. Here we show that the neonatal brain can learn to discriminate natural vowels from backward vowels, a contrast unlikely to have been learnt in the womb. Using functional near-infrared spectroscopy, we examined the neuroplastic changes caused by 5 h of post- natal exposure to random sequences of natural and reversed (backward) vowels (T1), and again 2 h later (T2). Neonates in the experimental group were trained with the same stimuli as those used at T1 and T2. Compared with controls, infants in the experimental group showed shorter haemodynamic response latencies for forward vs backward vowels at T1, maximally over the inferior frontal region. At T2, neural activity differentially increased, maximally over superior temporal regions and the left inferior parietal region. Neonates thus exhibit ultra-fast tuning to natural phonemes in the first hours after birth.