A series of azo-type side-chain liquid c ystalline polysiloxanes (AZLCPs) were synthesized, starting from organic polysiloxane and azo-type mesogenic compounds having an end ally1 group. The AZLCPs were further used to coordinate with palladium dichloride and potassium chloride, by which a series of palladium complexes of AZLCPs (Pd-AZLCPs) were prepared. The mesogenic properties of all of the liquid crystalline polymers were characterized by using differential scanning calorimetry, polarized microscope and wide-angle X-ray diffraction. It was found that all of the polymer ligands and their palladium complexes showed thermotropic liquid c ystallinity and that the incorporation of the palladium ions gave positive effects to the mesogenic properties of their polymer ligand counterpart. Cpmpared with the corresponding AZLCPs, the Pd-AZLCPs have higher isotropization temperatures and a broader mesophase temperature range. The mesogenic properties of the liquid crystalline polymer ligands and their palladium complexes were also varied gradually by changing the length of the alkoxy groups on the side chain. The polymers that have a color emissive group and a highly flexible polysiloxane main chain may potentially be used as nonlinear optical materials.