The invention provides a chrome-free insulating coating composition and a preparation method and an oriented silicon steel plate. The coating composition comprises the following components of, by weight, 100 parts of phosphate solutions, 1-5 parts of molybdate, 50-150 parts of silica sols, 3-13 parts of selenium dioxide, 1-10 parts of metallic oxide and/or metal hydroxide, 5-15 parts of organic acid, 1-6 parts of boric acid and 100-300 parts of water. The preparation method of the composition comprises the steps that the phosphate solutions, the boric acid and the water are added; the selenium dioxide and the organic acid are sequentially added; and the metallic oxide and/or metal hydroxide and the molybdate are added, then the silica sols are added, and the composition is obtained. The oriented silicon steel plate comprises a pedestal and a chrome-free insulating coating formed on the surface of the pedestal, and the chrome-free insulating coating is obtained by coating the chrome-free insulating coating composition on the surface of the pedestal. The chrome-free insulating coating has extremely high interlayer resistance, surface hardness and surface tension and shows the excellent magnetic property improved effect.