New through-space cyano-substituted poly(p-arylenevinylene)s containing a [2.2]paracyclophane unit were synthesized by the Knoevenagel reaction. Polymers 5 and 7 have cyano groups at alpha-positions and beta-positions from the dialkoxyphenylene unit, respectively. Their optical and electrochemical behaviors were investigated in detail in comparison with their model compounds. Polymers 5 and 7 exhibited through-space conjugation via the cyclophane units. Polymer 5 showed greenish blue emission (lambda(max) = 477 nm) in diluted solution with fluorescence quantum efficiency (Phi(F)) of only 0.007, whereas polymer 7 emitted in the bluish green region (lambda(max) = 510 nm) with Phi(F) of 0.32. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5979-5988,2009