Based on the dual mechanisms of control (DMC) theory, there are two distinct mechanisms of cognitive control, proactive and reactive control. Importantly, accumulating evidence indicates that there is a developmental shift from predominantly using reactive control to proactive control during childhood, and the engagement of proactive control emerges as early as 5-7 years old. However, less is known about whether and how proactive control at this early age stage is associated with children's other cognitive abilities such as working memory and math ability. To address this issue, the current study recruited 98 Chinese children under 5-7 years old. Among them, a total of 81 children (mean age = 6.29 years) contributed useable data for the assessments of cognitive control, working memory, and math ability. The results revealed that children at this age period predominantly employed a pattern of proactive control during an AX-Continuous Performance Task (AX-CPT). Moreover, the proactive control index estimated by this task was positively associated with both working memory and math performance. Further regression analysis showed that proactive control accounted for significant additional variance in predicting math performance after controlling for working memory. Most interestingly, mediation analysis showed that proactive control significantly mediated the association between working memory and math performance. This suggests that as working memory increases so does proactive control, which may in turn improve math ability in early childhood. Our findings may have important implications for educational practice.