A series of polyesters with,T-conjugated donor-acceptor segments was synthesized by the condensation of azobenzene-4,4'-dicarbonylchloride with 1,4:3,6-dianhydro-D-sorbitol ([alpha](D)(25) = + 42.5degrees) and biphenolic chromophores, bis(4-hydroxyphenylazo)-2,2'-dinitrodiphenylmethane and bis(4-hydroxyphenylazo)-2,2'-dinitrodiphenylsulfone. The polymers were characterized by spectral methods (IR, ultravioletvisible, and NMR), thermal methods (thermogravimetry and differential scanning calorimetry), wide-angle X-ray scattering, and polarimetry. The polymers containing isosorbide units were optically active and crystalline. They exhibited glass-transition temperature values between 100 and 160degreesC and were stable up to 400degreesC. The second-harmonic generation (SHG) efficiency of the polymers was experimentally verified by a powder-reflection technique with 2-methyl-4-nitroaniline as a reference. The SHG efficiencies of the polymers were compared to those of the chromophores and explained as a function of the percentage of chiral composition. The hyperpolarizability beta values were also determined by a two-level model solvatochromic method and computational methods.