The microspheres, nanowires, and butterfly-like structures of poly(9,9-dihexylfluorene) were fabricated by a novel approach, namely, the nonsolvent vapor method (NSVM). The controlled formation of the micro- and nanostructures was well discussed, and the assembly model was proposed. A superhydrophobic film with butterfly-like structures was obtained. The NSVM was found to be useful in forming organic optoelectronic devices that were less sensitive to water. This led to a simple, rapid, and novel method for the formation of pi-conjugated polymers without further functionalization.