The molecular hyperpolarizabilities and electronic properties of some azulene-containing chromophores have been investigated by employing AM1/FF and ZINDO/S-CI approaches. The calculation results show good agreement with the experimental values. It is found that the nonalternant azulene ring can be regarded as a more efficient conjugation bridge compared with benzene and thiophene because of its lower delocalization energy. Enhanced beta values can be obtained by extending the conjugation length, altering substituted positions, or choosing appropriate substituents. The 1-donor-5-acceptor-azulenes are found to have large beta values and small dipole moments (e.g., the 1-dithioylidenemethyl-5-[2,2-dicyanovinylbutadienyl] azulene has a high beta(0) value of 181.7 x 10(-30) esu, which is close to the highest reported values and a relatively small dipole mu of 5.3 D), and the latter properties may be helpful in reducing chromophore-chromophore electrostatic interactions and in optimizing the chromophore loading level and the order parameter while incorporated into the polymer matrix.