Humans are unique in developing large lexicons as their communication tool. To achieve this, they are able to learn new words rapidly. However, neural bases of this rapid learning, which may be an expression of a more general cognitive mechanism, are not yet understood. To address this, we exposed our subjects to familiar words and novel spoken stimuli in a short passive perceptual learning session and compared automatic brain responses to these items throughout the learning exposure. Initially, we found enhanced activity for known words, indexing the ignition of their underlying memory traces. However, just after 14 min of learning exposure, the novel items exhibited a significant increase in response magnitude matching in size with that to real words. This activation increase, as we would like to propose, reflects rapid mapping of new word forms onto neural representations. Similar to familiar words, the neural activity subserving rapid learning of new word forms was generated in the left-perisylvian language cortex, especially anterior superior-temporal areas. This first report of a neural correlate of rapid learning suggests that our brain may effectively form new neuronal circuits online as it gets exposed to novel patterns in the sensory input. Understanding such fast learning is key to the neurobiological explanation of the human language faculty and learning mechanisms in general.