The present study evaluated if lexical expertise, defined as the quality and quantity of a reader's word representations, influenced college students' ability to learn novel homophones while reading. In two experiments novel homophones (e.g. 'brale') and novel nonhomophones (e.g. 'gloobs') were embedded in sentences. In Experiment 1, novel homophones had low-frequency familiar word mates, and in Experiment 2 they had high-frequency familiar word mates. Learning was assessed with meaning and spelling recognition post-tests. Although eye movements during reading did not differ between the word types, participants had more difficulty learning the spellings of the novel homophones compared to the novel nonhomophones in Experiments 1 and 2. In contrast, participants only had difficulty learning the meaning of novel homophones when it had a low-frequency mate. Higher levels of lexical expertise were related to higher learning rates of novel homophone spellings only when the novel homophones had a high-frequency mate. Phonology is activated when novel words are encountered and can interfere with learning under certain circumstances.