Two experimental word-learning tasks were used to investigate the effect of exposure to rhyming words on L2 word learning among 120 fourth-grade Chinese-speaking children. The children were divided into four groups. Two groups were randomly assigned to a pre-exposure word-learning task and the other two a direct word-learning task. In the pre-exposure word-learning task, one group of children were told a story containing words which rhymed with the target words to be learned whereas the other group heard a story containing words that did not rhyme with the target words. In the direct word-learning task, one group directly learned three rhyming words without pre-exposure to rhyming words in a story and some directly learned three non-rhyming words. The results revealed that pre-exposure to rhyming words embedded in a story did not affect children’s new word learning. However, learning rhyming words together facilitated free recall and word-referent association in a production task. These results suggest that phonological manipulation in the rime unit of the new words provides a cue to the phonological shape of the new words, which facilitates the construction of phonological representations as well as the mapping of the representations to referents.