ZrO₂/PSS thin film with a high refractive index was fabricated on a glass substrate by a layer-by-layer self-assembly method. The surface morphology and thickness of the fabricated ZrO₂/PSS thin films were measured as a function of the number of (ZrO₂/PSS)n. As the number of (ZrO₂/PSS)n increased from n = 5 to n = 20, RMS roughness decreased from 29.01 nm to 8.368 nm. The ZrO₂ thin films exhibited high transmittance of 85% or more; and the 15-bilayer thin film exhibited the highest transmittance among the samples. The transmittance of the fabricated (ZrO₂/PSS)₁₅ thin film was ca. 90.8% in the visible range. The refractive index of the glass substrate coated by a (ZrO₂/PSS)₁₅ thin film with a thickness of 160 nm increased from ca. 1.52 to 1.74 at the 632 nm wavelength.