A binder-free attachment method for TiO2 on a substrate has been sought to retain high active photocatalysis. Here, we report a binder-free covalent coating of phase-selectively disordered TiO2 on a hydroxylated silicon oxide (SiO2) substrate through rapid microwave treatment. We found that Ti-O-Si and Ti-O-Ti bonds were formed through a condensation reaction between the hydroxyl groups of the disordered TiO2 and Si substrate, and the disordered TiO2 nanoparticles themselves, respectively. This covalent coating approach can steadily hold the active photocatalytic materials on the substrates and provide long-term stability. The binder-free disordered TiO2 coating film can have a thickness (above 38 mu m) with high surface integrity with a strong adhesion force (15.2 N) against the SiO2 substrate, which leads to the production of a rigid and stable TiO2 film. This microwave treated TiO2 coating film showed significant volatile organic compounds degradation abilities under visible light irradiation. The microwave coated selectively reduced TiO2 realized around 75% acetaldehyde degradation within 12 h and almost 90% toluene degradation after 9 h, also retains stable photodegradation performance during the cycling test. Thus, the microwave coating approach allowed the preparation of the binder-free TiO2 film as a scalable and cost-effective method to manufacture the TiO2 film that shows an excellent coating quality and strengthens the application as a photocatalyst under severe conditions.