The syllable and the phoneme are two important units in the phonological structure of speech sounds. In the brain mapping literature, it remains unsolved as to whether there are separate brain regions mediating the processing of syllables and phonemes. Using functional magnetic resonance imaging (fMRI), we investigated the neural substrate of these phonological units with Chinese subjects. Results revealed that the left middle frontal cortex contributes to syllabic processing, whereas the left inferior prefrontal gyri contributes to phonemic processing. This pattern of findings offers compelling evidence for distinct cortical areas relevant to the representation of syllables and phonemes. Hum. Brain Mapping 18:201–207, 2003. © 2003 Wiley-Liss, Inc.