Rhyme, which is ubiquitous in the language experiences of young children, may be especially facilitative to vocabulary learning because of how it can support active predictions about upcoming words. In two experiments, we tested whether rhyme, when used to help children anticipate new words would make those words easier to learn. Two- to 4-year-old children heard rhyming stanzas naming novel monsters under three conditions: A non-rhyme condition in which novel monster names appeared as unrhymed elements within a rhymed stanza, a non-predictive rhyme condition in which the novel names were the rhymed element in the first line of a stanza, and a predictive rhyme condition in which the monster name came as the rhymed element in the last line of the stanza after a description of the features that distinguished him. In tests of retention and identification children showed greatest novel name learning in the predictive rhyme condition in both between-subjects (Experiment 1) and within-subjects (Experiment 2) comparisons. Additionally, when parents acted as the storybook readers in Experiment 2, many of them distinctly paused before target words in the predictive rhyme condition and for their children a stronger predictive rhyme advantage surfaced. Thus rhyme is not only facilitative for learning, but when the novel vocabulary is specifically in a position where it is predictable from the rhymes, it is most accessible.