Human populations show large individual differences in math performance and math learning abilities. Early math skill acquisition is critical for providing the foundation for higher quantitative skill acquisition and succeeding in modern society. However, the neural bases underlying individual differences in math competence remain unclear. Modern neuroimaging techniques allow us to not only identify distinct local cortical regions but also investigate large-scale neural networks underlying math competence both structurally and functionally. To gain insights into the neural bases of math competence, this review provides an overview of the structural and functional neural markers for math competence in both typical and atypical populations of children and adults. Although including discussion of arithmetic skills in children, this review primarily focuses on the neural markers associated with complex math skills. Basic number comprehension and number comparison skills are outside the scope of this review. By synthesizing current research findings, we conclude that neural markers related to math competence are not confined to one particular region; rather, they are characterized by a distributed and interconnected network of regions across the brain, primarily focused on frontal and parietal cortices. Given that human brain is a complex network organized to minimize the cost of information processing, an efficient brain is capable of integrating information from different regions and coordinating the activity of various brain regions in a manner that maximizes the overall efficiency of the network to achieve the goal. We end by proposing that frontoparietal network efficiency is critical for math competence, which enables the recruitment of task-relevant neural resources and the engagement of distributed neural circuits in a goal-oriented manner. Thus, it will be important for future studies to not only examine brain activation patterns of discrete regions but also examine distributed network patterns across the brain, both structurally and functionally.