The invention relates to a photocatalytic self-cleaning coating as well as a preparation method and application thereof, the photocatalytic self-cleaning coating is prepared from a photocatalytic material, a nano SiO2 film forming material, a coating regulator and a solvent, and is characterized by being prepared from the photocatalytic material, the nano SiO2 film forming material, the coating regulator and the solvent, a film layer formed by coating has photocatalytic self-cleaning, anti-reflection and anti-reflection and surface hardening functions; the coating comprises the following components in percentage by mass: 0.2%-2% of a photocatalytic material, 3%-8% of a nano SiO2 film forming material, 0.01%-0.2% of a coating regulator and 90%-95% of a solvent, the photocatalytic material is a composite material of carbon, nitrogen and phosphorus doped nano TiO2 and phosphorus doped active g-C3N4, and is formed by polymerizing and activating a mixture of carbon, nitrogen and phosphorus doped nano TiO2 gel, urea, melamine and phosphoric acid and performing ultrasonic stripping in an ethanol solvent; the nano SiO2 film forming material is acidic hydrosol of methyl silicone resin and tetraethoxysilane. The photocatalytic self-cleaning coating disclosed by the invention can prevent the surface of solar cell glass from being polluted, and the light transmittance and the surface hardness are improved.