The azimuthal anchoring energy and pretilt angle of a nematic liquid crystal (E7) which was aligned on a thin layer of polyimide (PI) and poly(vinyl cinnamate) (PVCi) blend by the irradiation of polarized UV on the surface, were studied. Within a PVCi content of 10–100 wt%, the azimuthal anchoring energy remains unchanged with the decrease of the PVCi content in the blend, which is attributed to the preferential occupation of the surface by cinnamate chromophore. The blend alignment layer revealed a significantly enhanced thermal stability of azimuthal anchoring in comparison with the pure PVCi based alignment layer on account of the stiffening of the layer by the incorporated PI, which caused low thermal relaxation of the structural anisotropy developed from PVCi in the blend. The addition of PI into PVCi was also found to be effective for improving the thermal stability of the pretilt angle.