The copolymers consisting of chiral (S)-(−)-1-(4-nitrophenyl)pyrrolidin-2-yl]methyl 2-methacrylate ((S)-PYM) and azobenzene methacrylic co-monomers: 2-(methyl{4-[(E)-(5-methylisoxazol-3-yl)diazenyl]phenyl}amino)ethyl 2-methacrylate (ISM) or 2-{[4-[4-{(2,6-dimethylpirymidin-4-yl)amino]sulfonyl}phenyl) diazenyl]phenyl}-(methyl)amino]ethyl 2-methacrylate (SUM) were synthesized by radical polymerization. The quantum chemical calculations were carried out to predict spectral and nonlinear optical properties of the materials in question. The copolymers showed reversible photochromic properties under illumination with light by change of UV–vis spectra and ellipsometric parameters. The ellipsometric measurements made it possible to determine the change of refractive index under illumination that was in the range between 0.017 and 0.041 depending on copolymer type. Photochromic gratings were inscribed on the surface of polymer films in two kinds of experiments, leading to interesting conclusion that the surface relief grating could be recorded by two interfering laser beams as well as by a single linearly polarized laser beam. The chirooptical properties of the materials were investigated by circular dichroism spectroscopy.