Uneven structures on hair fiber surface, such as lift up of cuticle or build up of hair spray ingredients, generally cause a diffuse reflection which results in a dull and unhealthy appearance. However, in the case of finer structure than wavelength of visible light, the optical properties change significantly. An application of the phenomenon to hair care products is reported in this paper. Formation of the fine structure on hair surface was achieved by only a shampoo and rinse-off conditioner system including amino-silicone. Chroma enhancement of hair and light introduction into hair fibers were observed simultaneously with formation of the fine structure on the hair surface. The light introduction phenomenon is understood in terms of "Effective Medium Approximation" (EMA). The simulation study based on EMA indicates that a very low refractive index surface is expected to be realized, which well explains the optical experimental results. When the shampoo and conditioner system developed to form the structure on fiber surface was applied to dyed hair, enhancement and long-lasting of vivid appearance was confirmed in spite of dye elution.