Acrylate-terminated poly(beta-amino esters) are cross-linked to form materials useful in the medical as well as non-medical field. The polymeric starting material is combined with a free radical initiator, either a thermal initiator or a photoinitiator, and the mixture for cross-linking is heated or exposed to light depending on the initiator used. The resulting materials due to the hydrolysable ester bond in the polymer backbone are biodegradable under physiological conditions. These cross-linked materials are particular useful as drug delivery vehicles, tissue engineering scaffolds, and in fabricating microdevices. The materials may also be used as plastics, coating, adhesives, inks, etc. The cross-linked materials prepared exhibit a wide range of degradation times, mass loss profiles, and mechanical properties. Therefore, the properties of the material may be tuned for the desired use. The high-throughput approach to preparing a library of cross-linked poly(beta-amino esters) allows for the rapid screening and design of degradable polymers for a variety of applications.