Thin films of Si heavily doped with Mn impurities at nonequilibrium doping levels have been successfully prepared by Laser-Ablation MBE. The electronic structure of Mn-doped Si thin films have been investigated by Auger Valence Electron Spectroscopy (AVES). The peak positions of Mn[3p,V,V] (V=3d) Auger spectra of Si:Mn thin films were located at the higher energy region than those of pure Mn and Mn 5Si 3 compound. For the Si:Mn thin film grown on SiO 2/Si(001) substrate, the new Auger peak was observed around 50 eV. The changes of the line shape were observed in Mn[L,M,M] (L=2s,2p; M=3s,3p,3d) Auger spectra of Si:Mn thin films compared with those of pure Mn and Mn 5Si 3 compounds. In the Mn[2s,M,V] (M=3s,3p,V=3d) spectra for Si:Mn thin films, the new peaks were appeared around 700 eV. These new peaks were considered to arise from the new split of the 3d electron states due to the formation of the Mn–Si bonds in Si:Mn thin films.