The present study was carried out to investigate whether sign language structure plays a role in the processing of complex words (i.e., derivational and compound words), in particular, the delay of complex word reading in deaf adolescents. Chinese deaf adolescents were found to respond faster to derivational words than to compound words for one-sign-structure words, but showed comparable performance for two-sign-structure words. For both derivational and compound words, response latencies to one-sign-structure words were shorter than to two-sign-structure words. These results provide strong evidence that the structure of sign language affects written word processing in Chinese. Additionally, differences between derivational and compound words in the one-sign-structure condition indicate that Chinese deaf adolescents acquire print morphological awareness. The results also showed that delayed word reading was found in derivational words with two signs (DW-2), compound words with one sign (CW-1), and compound words with two signs (CW-2), but not in derivational words with one sign (DW-1), with the delay being maximum in DW-2, medium in CW-2, and minimum in CW-1, suggesting that the structure of sign language has an impact on the delayed processing of Chinese written words in deaf adolescents. These results provide insight into the mechanisms about how sign language structure affects written word processing and its delayed processing relative to their hearing peers of the same age.