Structurally different alcohols, e.g. 1,4-cyclohexanedimethanol, 1,1,1-tris(hydroxymethyl)propane, hydroquinone, and bisphenol A, were used for photocross-linking of glycerol diglycidyl ether on purpose to study structure-properties relationship of the resulting polymer films. Kinetics of photocross-linking was investigated by photorheometry. Dependencies of chemical structure and amount of alcohol used on mechanical, thermal, rheological properties, and biodegradability of the synthesized polymers were studied. The addition of alcohol resulted in an increase of the rate of photocross-linking of glycerol diglycidyl ether. The amount of alcohol used had more considerable effect on properties of polymers than chemical structure of alcohol. The higher amount (>20 mol%) of alcohol led to the easier association of alcohol molecules with released protons and thus deteriorated the properties of the cross-linked polymers. However, the addition of alcohols increased the biodegradability of resulted polymers.