Poly(2,5-dioctyloxy-p-phenylene) was fabricated into Chrysanthemum-like, rose-like, and coil-like micro-nanostructures and porous sponge-like three-dimensional (3D) network via solution-phase self-assembly by two types of phase separations (continuous and dispersed phases) occurred by the dissolution of polar MeOH vapor and nonpolar hexane vapor into the polymer solutions, respectively. Morphological changes of polymers produced significant changes in the optical properties. It was concluded that the choice of a good solvent and nonsolvent vapor for hairy-rod polymers is a facile way to design and fabricate various super-macromolecular architectures. (C) 2016 Elsevier B.V. All rights reserved.