Initial oxidation by high purity ozone and molecular oxygen of Si(111)7x7 was investigated by second harmonic generation (SHG) with a 1.064 mu m Nd:YAG laser. Decrease of second harmonics (SH) intensity to almost zero after 5 L ozone gas exposure, in spite of the fact that molecular oxygen kept SH intensity for the same amount of exposure, indicated that ozone is inserted into the Si-Si backbond in the subsurface layers more effectively than molecular oxygen. In the initial exposure, rates of rapid decrease in SH intensity for both ozone and oxygen adsorption were in the same order of magnitude, although O 1s x-ray photoelectron spectroscopy (XPS) intensity showed high reactivity of ozone. This is because of a difference in the information depth between SHG and XPS so that oxygen species in the subsurface layers are not effective in decreasing SH intensity. This indicates that the process of attacking backbonds is underway even with an initial exposure of <5 L.