This study investigated the roles of associative learning and linguistic knowledge, in particular phonological and semantic knowledge, in word learning of Chinese readers using a cross-sectional design. Extending past research in associative learning using existing Chinese characters as word stimuli, this study resorted to pseudowords and invented words to control for participants' possible experience with the word stimuli. Fifty-three Chinese second graders and thirty Chinese undergraduates participated in the study. They were individually administered tasks of nonverbal reasoning, phonological memory, rapid automatized naming, Chinese word reading and associative learning. The results showed that associative learning significantly predicted Chinese word reading in both beginning and proficient readers, after controlling for phonological memory and rapid automatized naming. Also, a developmental trend in the facilitative effect of pre-exposure to linguistic knowledge on word learning was observed, such that no effect of pre-exposure was observed in the beginning readers, but a significant effect was observed in the proficient readers. This study contributes to a better understanding of word learning processes in Chinese reading development.