Background: Research has shown that paired associate learning (PAL) plays an important role in children's word reading across different languages. However, little is known about the construct of PAL and its relationship with word reading in Chinese children. Methods: A total of 204 second-year kindergarten children from Mainland China were assessed on measures of PAL, including the four mapping conditions of PAL -- visual-verbal, verbal-verbal, visual-visual and verbal-visual PAL. Tasks of working memory (WM), inhibitory control, visual-motor integration (VMI), phonological awareness, orthographic knowledge and Chinese word reading were also administered to these children. Results: Our results showed that WM, VMI and phonological awareness were unique predictors of PAL, whereas inhibitory control and orthographic knowledge were not. Furthermore, PAL showed an independent contribution to Chinese word reading after controlling for phonological awareness and orthographic knowledge. The mediation analysis showed that PAL was a significant mediator of the association between different cognitive-linguistic skills and Chinese word reading. Conclusion: Paired associate learning contributes to Chinese word reading over and above phonological awareness and orthographic knowledge. Findings underscore the potential importance of PAL, as distinct from other cognitive-linguistic skills, for understanding variability in early reading development.