A TiO₂/fluorined acrylic nano-composite paint is synthesized. A series of detection were conducted on the obtained resin product. The gel permeation chromatography (GPC) and differential scanning calorimetry (DSC) were applied to detect the weight-average molar mass (Mw) and glass transition temperature (Tg) of the fluorined acrylic resin. Fourier Transform Infrared Spectroscopy (FT-IR) analysis was used to determine successful grafting of nano-TiO₂ on resin, and the antifouling degree of the composite coatings was analyzed by the marine immersion test.The experimental results showed that the antifouling performance can be improved significantly by adding surface-modified nano-TiO₂. Therefore a toxin-free and eco-friendly preparation of marine antifouling paint was provided.