We report here a nonlinear band gap opening of graphene while varies the concentration of the co-doped B-N atoms. Measurements of X-ray absorption near edge structure (XANES) and X-ray emission spectra show an opening of band gap on graphene from 0 to 0.6 eV as the concentration of B-N dopant varying from 0 to 6%. Further increase on the doping level leads to a significant reduction on the band gap value. We demonstrate that such non-linear behavior is attributed to a change of the effect of B-N dopants on the electronic structure of grapheme. An locally redistributed π electronic state change by B-N dopant. The suggested physical picture is confirmed by the performed ab-initio calculation with considering the B-N structures obtained from experiments.