We present the efficient polymerization of a vinyl monomer bearing electron-transporting units, 2-[4-(4'-vinylbiphenylyl)]-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (vPBD), by using a TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl)-mediated radical polymerization method. A kinetic study using this monomer showed a quasi-living free radical character. The corresponding homopolymer was obtained in high yield with a very narrow polydispersity. Further reaction of the isolated polymer with another vinyl monomer bearing luminescent groups, 4-tert-butyl-4'-(4-vinylstyryl)-trans-stilbene (v3PV), gave a diblock copolymer containing both functional groups.