The present study investigated the effects of exposure to Chinese orthography on learning phonological forms of new words in learners of Chinese as a second language. A total of 30 adult learners of Chinese studied spoken label and picture associations presented either with phonologically accurate characters, characters with partial phonological information, or no orthography. Half the phonologically accurate or partially accurate characters were semantically transparent or opaque. Spoken labels were recalled without orthography presence. Results showed that exposure to phonologically accurate and semantically transparent characters during learning did not enhance the recall of the spoken labels compared to no orthography. But exposure to characters with partial phonological information and semantically opaque characters significantly hindered vocabulary learning. The implications for Chinese as a second language vocabulary acquisition and instruction are discussed.