Dual‐functional antifog/antireflection coatings with a special bi‐layer structure for plastic substrates were prepared. The superhydrophilic top layer was a crosslinked network of dipentaerythritol hexaacrylate (DPHA), hydrophilic agent (synthesized from Tween 20, isophorone diisocyanate, 2‐hydroxyethyl methacrylate), and organically modified silica. The high‐refractive‐index bottom layer was composed of TiO2 nanoparticles and DPHA. The two layers were chemically bonded through a UV‐curing process. By tuning the thicknesses of the two layers, a series of coatings were prepared. These coatings were highly transparent and able to reduce reflectance. In addition, they adhered well to the substrate, and demonstrated superb antifogging capability on steam tests. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48822.