We have observed spin splitting and band gap structure in the Si[110] direction by doping with impurities, which is manifested by a significant opening of the spin-splitting energy level in the localized states. Interestingly, the opening effect occurs such that the electronic spin states are embedded in the localized states on the surface. Here, the broken symmetry obviously appears in the system. In the simulation calculation, it is observed that the spin-splitting gap of the electronic spin levels can be opened over 500 meV in the localized states for the Si=O double bond for doped Si[110] nanowires with a diameter of 0.4 nm. Si[110] nanowire structures doped with oxygen were prepared on silicon wafers using a combination of nanosecond pulsed laser deposition (PLD) and coherent electron beam irradiation studied comparatively in experiments. By combining the experimental and computational results, the physical model on the coupling between the electronic spin states and the localized states was constructed, which will have good application potential in the fields of the electronic spin qubit, quantum information storage, and quantum information processing.