A simple method of preparing nanotemplates with special microstructures by polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) surface micelles was researched in this study. The self-assembly of surface micelles adsorbed on mica when exposed to the vapors of toluene, acetone and water was studied by atomic force microscopy (AFM) in detail. Results indicate the irregular and spherical structures can be obtained in the vapors of toluene and acetone respectively. Various microstructures ranging from starfish-like to chrysanthemum, torus, cylinder and hat structures can be obtained in water vapor for different time. The special microstructures of PS-b-PMMA can be used as nanotemplates to prepare nanomaterials with special nanostructures.