2,5-Dialkoxypoly(p-phenyleneethynylene) (3) functionalized with N-t-BOC-L-phenylalanine molecules was synthesized by Pd-catalyzed reaction of dioctyloxybis[(trimethylsilyl) ethynyl] benzene (1) with aromatic diiodide 2 linked to two amino acid units by six carbon atoms alkoxy chains. Optical properties were investigated both in solution and in the solid state (as thin films) by absorption, fluorescence and chiroptical spectroscopies (CD and CPL). Polymer 3, that represents one of few fully characterized dialkoxy-substituted PAEs, is also the first example of a poly(aryleneethynylene) (PAE) with amino acidic chiral pendants.