H-Bonded semifluorinated dendritic polymer networks are generated by association of macromolecules, driven by the weak diaminopyridine (DAP) and thymine (THY) couple. Solvent-dependent morphologies are observed: a continuous film structure when drop-cast from tetrahydrofuran (THF) solution or uniform nanoparticles with a diameter of ∼50 nm in toluene.