A small series of amino oligo-phenylenevinylenes (OPVs) were successfully synthesized from their nitro-analogs in a rapid, simple, and highly efficient fashion employing a sodium sulfide/pyridine system as a reducing agent. In this research, classic and sustainable reduction methodologies including NH4HCO2/Zn and a choline chloride/tin (II) chloride deep eutectic solvent (DES) were also evaluated, showing degradation products, incomplete reactivity, and product isolation difficulties in all cases. The straightforward Na2S/pyridine synthetic protocol proved to maintain the E-E stereochemistry of the OPV backbone that has been previously assembled by the Mizoroki–Heck cross-coupling reaction. Also, the optoelectronic properties were determined and discussed, considering the amino group insertion in these conjugated systems as a contribution for future construction of novel materials with applications in supramolecular electronics, light harvesting, and photocatalysis.