Under nonsolvent vapor atmospheres, poly(1,1'-binaphthol butyl ether) nanospheres can be self-assembled from various good solvent solutions. To obtain the optimized assembling parameters, the factors such as the solvents and the polymer concentrations, on the formation of polymeric nanospheres were investigated. The choice of good solvent and nonsolvent is an important factor. The well-ordered nanospheres with the sizes of hundreds nm can be easily obtained from the preparation combinations such as CH2Cl2/MeOH vapor, CHCl3/MeOH vapor, CHCl3/EtOH vapor, and THF/EtOH vapor. Moreover, the increasing polymer concentration leads to the increasing spherical agglomerations. The static water contact angles of the films with polymeric spheres were measured to be above 130A degrees. With the excitation wavelength of 371 nm, the polymeric nanospheres showed the blue emission with the peak at 480 nm. The nonsolvent vapor method is a facile way to prepare polymeric nanospheres.