Lithium-ion batteries (LIBs) have been dominant power sources for portable electronics and electric vehicles (EVs). However, the shortage of the natural abundance and biased global distribution of lithium (Li) resources may present unavoidable challenges in the future. As such, Na- and K-ion batteries (NIBs and KIBs) have attracted attention to diversify the power sources. Graphite is the most widely used anode material for commercial LIBs based on the Li-ion intercalation mechanism. However, the capacities of graphite as Na- and K-ion insertion host is limited than that of Li. In this study, we show that graphene is a promising candidate to store Na and K-ions through a surface-controlled charge mechanism. We correlate the charge storage capacity for alkali metal ions with their binding energy on the graphene surface. We systematically modify the structure of graphene to improve the charge storage capacity for Na- and K-ion storage. Finally, we reveal that graphene can efficiently store Na and K ions through the surface-controlled capacitive mechanism, exhibiting the enhanced rate-capability and excellent cycling stability.