In recent days, additive manufacturing technologies (AMT) based on photopolymerization have also found application in tissue engineering. Although acrylates and methacrylates have excellent photoreactivity and afford photopolymers with good mechanical properties, their cytotoxicity and degradation products disqualify them from medical use. Within this work, (meth)acrylate-based monomers were replaced by vinyl esters with exceptional low cytotoxicity. The main focus of this paper lies on the determination of the photoreactivity and investigations concerning mechanical properties and degradation behavior of the new materials. Tested monomers provide sufficient photoreactivity for processing by AMT. Mechanical properties similar to natural bone could be obtained by adding suitable fillers like hydroxylapatite (HA). The right ratio of hydrophobic and hydrophilic monomers allows the tuning of the degradation behavior. Finally, with the optimum formulation, cellular 3D structures were built using digital light processing. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.