Novel modifications of the synthetic polymer poly(vinyl alcohol) (PVA) were developed for application in the field of biomedical engineering. PVA was modified with allyl succinic anhydride, norbornene anhydride as well as with c-thiobutyrolactone to produce macromers with reactive ene and thiol groups, respectively. Cytotoxicity studies have shown that the material exhibits almost no cell-toxicity, when used in concentrations of 1 and 0.1 wt % for 24 h. The obtained macromers were photocrosslinked via thiol-ene chemistry. Storage stability of the macromer mixtures with different concentrations of pyrogallol as stabilizer were investigated. Photorheometry was employed to optimize mixtures concerning reactivity based on their thiol-to-ene ratio, photoinitiator concentration, and macromer content. The crosslinked hydrogels were studied concerning their swellability. To form hydrogels with cellular structure two-photon-polymerization (2PP) was employed. Processing windows for 2PP of selected mixtures were determined. (C) 2016 Wiley Periodicals, Inc.