This paper examines the influences of solvent evaporation and atmosphere humidity on self-assembling structures and thin-film microscopic morphologies of amphiphilic rod-coil block oligomers (EOnOPV) containing conjugated oligo(phenylene vinylene) dimer (OPV) coupled to poly(ethylene oxide) (PEO; n, the average number of ethylene oxides, is 16, 12, 7, and 3, respectively) on hydrophilic substrates. Atomic force microscopy (AFM), UV-vis absorption, and small angle X-ray diffraction are employed to investigate the thin-film morphology and structure. Solvent evaporation and atmosphere humidity are found to exert a strong influence on thin-film morphology and structure. Under the condition of quick evaporation and dry atmosphere, all EOnOPV oligomers form the monolayer islands. Increasing the solute volume, both EV16OPV and EO12OPV oligomers can form the polar lamellas with a head-to-tail packing arrangement. Under the condition of slow evaporation and humid atmosphere, EO16OPV and EO12OPV may self-assembly into curvy nanoribbons with well-defined width and curvature radii on mica, while EO7OPV and EO3OPV with the shorter PEO coils do not form. A symmetric bilayer structure for the ribbons is proposed. Plausible reasons for the variation in thin-film morphology are discussed, based on the results obtained from investigation of PEO coil length, solvent evaporation, and atmosphere humidity effects. (c) 2005 Elsevier Inc. All rights reserved.