In the present study, we investigate the irradiation-defects hybridized graphene scaffold as one potential building material for the anode of Li-ion batteries. Designating the Wigner V2(2) defect as a representative, we illustrate the interplay of Li atoms with the irradiation defects in graphene scaffolds. We examine the adsorption energetics and diffusion kinetics of Li in the vicinity of a Wigner V2(2) defect using density functional theory calculations. The equilibrium Li adsorption sites at the defect are identified and shown to be energetically preferable to the adsorption sites on pristine (bilayer) graphene. Meanwhile, the minimum energy paths and corresponding energy barriers for Li migration at the defect are determined and computed. We find that, while the defect is shown to exhibit certain trapping effects on Li motions on the graphene surface, it appears to facilitate the interlayer Li diffusion and enhance the charge capacity within its vicinity, because of the reduced interlayer spacing and characteristic symmetry associated with the defect. Our results provide critical assessment for the application of irradiated graphene scaffolds in Li-ion batteries.