The synthesis of triphenylamine-based oligo(arylenevinylene)s was accomplished by Pd-catalyzed one-pot coupling of styrenes and tris(4-bromophenylamine). These oligo(arylenevinylene)s are characterized by temperature-induced crystallization in bulk but are amorphous in guest-host systems with polysulfone from which high-quality films for optical applications were obtained. The photoluminescence spectra of the oligo(arylenevinylene)s differed significantly in different solvents as well as in different polymer hosts which is of interest for multicolored LEDs.