The synthesis and the chemical physical characterization of new photoluminescent (PL) chromophores and polymers are reported. Chromophores (oligo-PPV symmetric derivatives ending with amino groups) are strong blue emitters with a PL quantum yield of similar to 70% in dioxane solution. They have been used to prepare polyamides by reaction with aliphatic acyl dichlorides in which emitting and non emitting units are alternated. PL properties of the synthesized polyamides have been evaluated in solution and reveal a strong blue emission (PL quantum yield similar to 60%), To increase the solubility of these systems, oligomers have been purposely prepared and then characterized. They show a peculiar white emission when excited in DMF solution; to get insight into this interesting behavior, asymmetric monoacetylated chromophores have been prepared as model compounds for the chromophoric end groups of the polyamide chains. The emission spectra of these compounds reveal a broad excimeric yellow emission which is responsible, along with the blue emission of the inner chromophoric units, of the overall white emission of the oligomers. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2677-2689, 2009