Anionic polymerizations of acrylates possessing 1-pyrenyl (Py1), 1-naphthyl (Np1), 2-naphthyl (Np2), and 2-fluorenyl (Fl2) groups as alpha-substituents were investigated as well as the properties of the obtained polymers. Py1 and Np1 did not undergo polymerization, whereas Np2 and Fl2, annulated alpha-phenylacrylates at 3,4-position of the phenyl group, afforded homo-oligomers and alternating copolymers with methyl methacrylate (MMA). The oligomer of Fl2 [oligo(Fl2)] exhibited strong excimer emission in diluted solution. In contrast, dominant monomer emission was observed for the alternating copolymer with MMA [ poly(Fl2-co-MMA)]. In the alternating copolymer, MMA units could function as spacers preventing the association of pendant fluorene moieties to suppress the excimer formation. (C) 2014 Wiley Periodicals, Inc.