A new class of photoactive poly(hydroxyl-amino ether)s P1a-d & P2a-d based on diarylidene-epoxy moieties were synthesized by ring opening polymerizations of diarylidene epoxy monomers 2a-d during the reaction with 4,4'-diamino diphenyl methane (DDM) or 4,4'-diamino diphenyl ether (DDE). Diarylidene-epoxy monomers 2a-d were synthesized by the reaction of diarylidene cycloalkanones derivatives 1a-d with excess of epichlorohydrin in presence of NaOH and TBAI as a catalyst. The molar masses of the resulting polymers were determined by gel permeation chromatography (GPC), all polymers have moderate molar masses. Moreover, the photo-responsive properties of selected examples of polymers were tested in THF by studying the photolysis of their solutions in THF under UV lamp (450 nm) at different time intervals. This study revealed the occurrence of photocrosslinking behavior in the system under these conditions. The thermal properties of these polymers were evaluated by thermogravimetric analysis (TGA). In addition, the morphological properties of selected examples of polymers were tested using scanning electron microscope (SEM).