Synthetic strategies towards appropriate symmetric and unsymmetric functionalization of the naphthalene ring are presented. By means of Knoevenagel and Wittig condensation reactions new fluorescent, differently functionalized oligo(2,6‐naphthylenevinylene)s have been synthesized, the presence of terminal aldehyde or bromine substitution opening the way to the incorporation of the fluorescent trimers in a variety of polymeric materials. The effect of substituting the phenylene ring by the more bulky dialkoxynaphthalene system in arylenevinylene‐type materials is studied from the structural point of view and the possibility to tune the emission color and the electron affinity through the introduction of naphthylenevinylene and cyano‐substituted naphthylenevinylene units is also investigated.