Surface pattern on the nano-and microscale is of great interest due to its special optical effect, which might find potential application in optical devices such as LCD display, packaging of LED chip, and thin-film solar cell. We here developed a facile bottom-up approach to fabricate microprotuberance (MP) on surface by using curable resin via sequential photocuring at room temperature and thermal polymerization at high temperature. The curable resin is composed of random fluorinated polystyrene (PSF) as blinder and trimethylolpropane trimethacrylate (TMPTA) as cross-linker. The polymerization of TMPTA during the annealing process at high temperature induces phase separation between the PSF and TMPTA cross-linked network, resulting in the extrusion of PSF and the formation of protuberance on the surface. The formation mechanism of MP was studied in detail by investigating the effect of annealing time, temperature, thickness of film, and PSF on the size and morphology. MPs with size from one to tens of micrometers were fabricated through this one-pot strategy. Moreover, encapsulation of integrated GaN/InGaN-based LED chip by the cross-linked coating with MP can enhance the light extraction efficiency and light diffusion obviously.