We measured brain activity in 12 adults for the repetition of auditorily presented words and nonwords, before and after repeated exposure to their phonological form. The nonword phoneme combinations were either of high (HF) or low (LF) phonotactic frequency. After familiarization, we observed, for both word and nonword conditions, decreased activation in the left posterior superior temporal gyrus, in the bilateral temporal pole and middle temporal gyri. At the same time, interaction analysis showed that the magnitude of decrease of activity in bilateral posterior temporal lobe was significantly smaller for LF nonwords, relative to words and HF nonwords. Decrease of activity in this area also correlated with the size of behavioral familiarization effects for LF nonwords. The results show that the posterior superior temporal gyrus plays a fundamental role during phonological learning. Its relationship to sublexical and lexical phonological processing as well as to phonological short-term memory is discussed.