"Subitizing" defines a phenomenon whereby approximately four items can be quickly and accurately processed. Studies have shown the close association between subitizing and math performance, however, the mechanism for the association remains unclear. The present study was conducted to investigate whether form perception assessed on a serial figure matching task is a potential non-numerical mechanism between subitizing ability and math performance. Three-hundred and seventy-three Chinese primary school students completed four kinds of dot comparison tasks, serial figure matching task, math performance tasks (including three arithmetic computation tasks and math word problem task), and other cognitive tasks as their general cognitive abilities were observed as covariates. A series of hierarchical regression analyses showed that after controlling for age, gender, nonverbal matrix reasoning, and visual tracking, subitizing comparison (subitizing vs. subitizing, subitizing vs. estimation) still contributed to simple addition or simple subtraction but not to complex subtraction ability or math word problem. After taking form perception as an additional control variable, the predictive power of different dot comparison conditions disappeared. A path model also showed that form perception fully mediates the relation between numerosity comparison (within and beyond the subitizing range) and arithmetic performance. These findings support the claim that form perception is a non-numerical cognitive correlate of the relation between subitizing ability and math performance (especially arithmetic computation).