Rapid automatized naming (RAN) is associated with children's arithmetic performance, which is multifactorial by nature and consists of arithmetic fluency, arithmetic procedure, and word problems. Yet, it is unclear whether RAN can predict all key aspects of arithmetic skills independently and what cognitive mechanisms may explain this relation. Using a sample of Chinese primary school students (N = 170), results showed that while RAN was associated with all key aspects of arithmetic skills, the relations of RAN--arithmetic procedure and RAN--word problems may be dependent on that of RAN--arithmetic fluency. Supporting the processing speed hypothesis, results further suggested that processing speed may underlie the relation between RAN and arithmetic performance. Findings made unique contribution to understanding the effect of RAN on arithmetic performance and cognitive mechanisms that may underpin this association in the context of Chinese culture.