A new class of linear unsaturated polyphosphate esters based on divanillylidene cyclohexanone possessing liquid crystalline-cum-photocrosslinkable properties have been synthesized from 2,6-bis[n-hydroxyalkyloxy(vanillylidene)]cyclohexanone [n = 6,8,10] with various alkyl/aryl phosphorodichloridates in chloroform at ambient temperature. The resultant polymers were characterized by intrinsic viscosity, FT-IR, H-1, C-13, and P-31-NMR spectroscopy. All the polymers showed anisotropic behavior under hot stage optical polarized microscope (HOPM). The liquid crystalline textures of the polymers became more transparent with increasing spacer length. The thermal behavior of the polymers was studied by thermogravimetric analysis and differential scanning calorimetry. The T-g, T-m, and T-i of the polymers decreased with increasing flexible methylene chain. The photocrosslinking property of the polymer was investigated by UV light/UV spectroscopy; the crosslinking proceeds via 2pi-2pi cycloaddition reactions of the divanillylidene exocyclic double bond of the polymer backbone. The pendant alkyloxy containing polymers show faster crosslinking than the pendant phenyloxy containing polymers. (C) 2004 Wiley Periodicals, Inc.