The present study examined the role of positional probability of syllables played in recognition of spoken word in continuous Cantonese speech. Because some sounds occur more frequently at the beginning position or ending position of Cantonese syllables than the others, so these kinds of probabilistic information of syllables may cue the locations of syllable boundaries in speech. Two word-spotting experiments were conducted to investigate the role of positional probability in the spoken word recognition process of Cantonese speech. It was found that listeners indeed made use of the positional probability of a syllable's onset but not of a syllable's ending sound in the spoken word recognition process. Together with other relevant studies in different languages, we propose that probabilistic phonotactics are one useful source of information in the spoken word recognition and speech segmentation process.