Neat poly(9,9-dioctyl-9H-fluorene) (PFO) and composites of PFO and a modified organonanosilica P(7) at weight ratios 90/10, 70/30, and 50/50 have been employed to prepare fluorescent and superhydrophobic coatings by spraying onto three different substrates: glass, Whatman paper, and a filtration membrane of mixed cellulose esters. The water repellency of the coatings and their photophysical properties are therein studied. It is found that, irrespective of the substrate and the composite composition, all coatings remain fluorescent. In some of the coatings prepared, confined morphologies are created, which fluoresce with a wavelength distribution resembling that of an ordered planar β-phase. Among the coatings prepared in this work, those with a ratio PFO/P(7) of 50/50 are the ones with the strongest chain confinement and the highest surface roughness, being highly emissive at the β-phase wavelengths and also superhydrophobic. Depending on the substrate these materials are also tough and flexible (cellulose based substrates) or display a remarkable light transmittance (glass). A final merit of these multifunctional materials is the simplicity of the preparation procedure, adequate for large surfaces and industrial applications.