Anisotropic diffractive gratings formed by birefringent molecular alignment are fabricated by a holographic technique using a photo-cross-linkable liquid crystalline copolymer (PLCCP). Depending on the exposure energy used for holographic recording, bright or dark regions of the interference fringe can be chosen for the molecularaligned region, analogous to positive-and negative-type photoresist processing in photolithography. In conjunction with simultaneously generated surface relief gratings, the anisotropic refractive index modulation inherent in the PLCCP film exhibits different diffraction properties depending on the incident beam polarization. The anisotropic refractive index grating profiles are quantitatively presented for two cases determined by the exposure energy, based on the Fourier analysis of diffractive optics. The selection of different grating formations selected by varying only the ex-A. Emoto ( ) posure energy could provide a strategy for the fabrication of functionalized diffractive optical elements.