Oxygen-defect vacancies that routinely exist in wet production of VO2 material or on the surface of VO2 single crystal after surface treatment have significant influence on the metal-insulator phase transition features mainly due to their enhanced effect of doping on V 3d electronic structure. The removal of the surface oxygen defects is highly desired for investigating the VO2 intrinsic electronic properties. In this work, we propose a charge transfer doping method by using strong electric affinity molecule tetrafluorotetracyanoquinodimethane (F4TCNQ) adsorption rather than the normal thermal annealing in oxygen atmosphere to heal the surface oxygen defects of VO2 crystalline film. The healing effect is probed by the electronic structure evolution at the F4TCNQ/VO2 interface. The VO2 crystalline film is grown by an oxygen plasma assisted molecular beam epitaxy method on an Al2O3(0001) substrate. Surface oxygen defects on VO2 film are produced after a mild sputtering with an ionic energy of 1 keV and a thermal annealing in vacuum at 100 ℃. The influence of F4TCNQ molecule adsorption on the electronic structure of the sputtered VO2 film is studied by using in-situ synchrotron-based photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS). XPS and XAS results demonstrate convincingly that V3+ species of sputtered VO2 are oxidized into the V4+ and simultaneously negative molecular ions form at F4TCNQ/VO2 interface resulting from the electron transfer from VO2 to the F4TCNQ layer. The preferred adsorption on surface defects and the strong electron withdrawing function of F4TCNQ molecules may account for the effective elimination of the electron doping effect of oxygen defects on VO2 surface. This charge transfer effect at interface recovers the electronic properties of VO2. Compared with thermal annealing in oxygen environment, the healing of oxygen defects by the molecular adsorption can prevent the surface from over oxidating VO2 into V2O5, which opens a new route to surface defect healing.