The synthesis, one- and two-photon absorption (TPA) and emission properties of two novel 2,6-anthracenevinylene-based copolymers, poly[9,10-bis(3,4-bis(2-ethylhexyloxy)phenyl)-2,6-anthracenevinylene-alt -N-octyl-3,6-carbazolevinyl-ene] (P1) and poly[9,10-bis(3,4-bis(2-ethylhexyloxy)phenyl)-2,6-anthracenevinylene-alt -N-octyl-2,7-carbazolevinylene] (P2) were reported. The as-synthesized polymers have the number-average molecular weights of 1.56 x 10(4) for P1 and 1.85 x 10(4) g mol(-1) for P2 and are readily soluble in common organic solvents. They emit strong bluish-green one- and two-photon excitation fluorescence in dilute toluene solution (Phi(P1) = 0.85, Phi(P2) = 0.78, lambda(em)(P1) = 491 nm lambda(em)(P2) = 483 nm). The maximal TPA cross-sections of P1 and P2 measured by the two-photon-induced fluorescence method using femtosecond laser pulses in toluene are 840 and 490 GM per repeating unit, respectively, which are obviously larger than that (210 GM) of poly[9,10-bis-(3,4-bis(2-ethylhexyloxy)phenyl)-2,6-anthracenevinylene], indicating that the poly(2,6-anthracenevinylene) derivatives with large TPA cross-sections can be obtained by inserting electron-donating moieties into the polymer backbone. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 463-470, 2010