Photosensitive main chain liquid crystalline poly (benzylidene-ether)s were synthesized by Claisen-Schmidt poly-condensation reaction of 4,4'-Diformyl-alpha,omega-diphenoxyalkanes with acetone, cyclopentanone and cyclohexanone. The diformyl precursors were synthesized from 4-hydroxybenzaldehyde and dibromoalkanes of varying spacer lengths. The structure of the monomers and polymers was confirmed by ELEM ANAL, Fourier transform infrared, H-1 NMR and C-13 NMR spectral analyses. Molecular weight of the polymers was determined by gel permeation chromatography and was found to be moderate. The thermogravimetric analysis data revealed that the polymers were stable up to 280 degrees C and start degrading thereafter. Cyclopentanone containing polymers are more stable than acetone and cyclohexanone containing polymers. The self-extinguishing properties of the synthesized polymers were studied by the determination of the limiting oxygen index values with Van Krevelen's equation. The influence of the length of methylene spacer on phase transition was investigated with differential scanning calorimetry and proved that the isotropic temperature decreases as the spacer length increases. Polarized optical microscopic study showed that cyclohexanone containing polymer IIIb exhibit nematic schlieren texture. Crystallinity of the polymers was studied with X-ray diffractograms. The photolysis of liquid crystalline poly(benzylidene-ether) s revealed that the entgegen, zusammen (EZ) photoisomerization proceeds in the system. Fluorescence spectra showed violet and green emission maxima. The band gap energy is calculated from absorption spectra are in the range of 3.17-3.40 eV. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 4809-4819, 2011