Nature provides us with a multitude of design solutions finely tuned by natural selection. Biomimetic, taking the shortcut of “Learning from Nature”, transfers optimum designs in nature to technical applications. Following a recent tide of researches on optical structures in biology, optical biomimetic thrives and yields various bioinspired optical materials with advanced optical properties mediated by microstructures borrowed from nature. This review covers optical biomimetic materials integrated with typical structural design based on multilayer, helicoidal structure, moth eye, photonic crystal, ridge, irregular network, double-facet microlens and tunable optical structures that lead to advanced optical effects including broad-angle structural color, color-mixing, polarization, antireflection, iridescence, ultra-blackness, ultra-whiteness, light focusing and dynamic structural color. The mechanisms underlying these structure-related optical phenomena have been described and the realization of corresponding biomimetic optical materials mimicking the natural structures has been elucidated. We conclude by making a prospect on optical biomimetic materials.