Theories of reading propose that the quality of word form representations affects reading comprehension. One claim is that synchronous retrieval of orthographic and phonological representations leads to better performance than asynchronous retrieval. Based on this account, one may hypothesize that synchronous rather than asynchronous presentation of orthographic and phonological forms should be beneficial when establishing the mapping between both, as it should lead to tighter couplings. We tested this hypothesis in two multi-session experiments, where participants studied isolated words of a tonal language unknown to them, Chinese. During study, written (using Pinyin transcription) and spoken word forms were presented simultaneously or in asynchronous fashion (audio-first, written-first). In both experiments, we observed an advantage for asynchronous over synchronous presentation at test, with audio-first presentation being most beneficial. These results suggest that the timing of written and spoken word forms has profound effects on the ease of learning a new tonal language.