Liquid-like anti-fouling coatings have broad application prospects in construction, automobiles, and ships due to their excellent surface protection properties, such as good anti-fouling and hydrophobic properties. In this study, a photo-curable material based on ethylene-thiol photoclick reaction was designed and investigated, which was composed of dipentaerythritol hexakis (3-mercaptopropionate) (DPEHMP), Octavinyl-cage polysesquisiloxane (APOSS), Mono-vinyl terminated polydimethylsiloxanes (Vi-PDMS), Phenylbis (2,4, 6-trimethylbenzoyl) phosphine as the photoinitiator and Dichloromethane as the solvent. Coatings derived from this photo-curable material were prepared, and the properties were studied. Upon exposure to ultraviolet photo (λ = 365 nm), cured liquid-like anti-fouling coatings were obtained. Through observation of the morphology of the anti-fouling coating, infrared spectroscopy measurement, and evaluation of the coating’s hydrophobic properties, a systematic study was conducted to investigate the effect of the dosage of Vi-PDMS on the anti-fouling performance of the coatings. Based on the above work, the photo-curable liquid-like anti-fouling coating formulation was further optimized, which laid a good foundation for its industrial application.