We here demonstrate a facile approach of one-step to obtain the complex wrinkling patterned surface of the photocuring coating by using thiol and fluorocarbon chains containing POSS (F-2-POSS-SH6) as reactive nanoadditive. F-2-POSS-SH6 can self-assemble into the top layer of the UV-curing liquid resin. As a result, the mismatch of shrinkage caused by the different types of photo-cross-linking reaction between the top layer and bulk layer leads to formation of the wrinkling pattern. The characteristic wavelength (lambda) and amplitude (A) are linearly dependent on the concentration of F-2-POSS-SH6. The resulting surface exhibits superlow surface energy (4.1 mN/m) when the concentration of F-2-POSS-SH6 is only 1%. The feasibility and generality of this approach for the excellent hydrophobic and oleophobic surface will undoubtedly find practical application in photocuring coating with functions such as self-cleaning.