New class of highly efficient polymers for liquid crystal (LC) photoalignment is proposed. These polymers are based on methacryloylaminoarylmethacrylates having two methacryloyl groups of different reactivity. The more active O-methacryloyl group is subjected to polymerization, while the less active NH-methacryloyl group undergoes photocrosslinking reaction in combination with Fries rearrangement. The latter process is anisotropic in case of polarized light irradiation that results in LC photoalignment with readily controlled pretilt angle and anchoring energy. The induced alignment shows high thermal and photo-stability.