Using first-principles method based on density functional theory, we perform a detailed study of the hydrogen storage properties of Li and Ca co-decorated graphene-like carbon nitride (g-CN) nanostructures. The results show that the average adsorption energy of the molecular hydrogen is ∼0.26 eV/H2, which is acceptable for reversible H2 adsorption/desorption near ambient temperature. Moreover, the findings also show that the storage capacity of the Li and Ca co-decorated g-CN can reach up to 9.17 wt %, presenting a good potential as hydrogen storage material. Regarding the H2 adsorption mechanism, it is demonstrated that the Li adatoms become positively charged through charge transferring to g-CN and then bind hydrogen molecules via the polarization mechanism.