The synthesis of multifunctional monomers that can be photopolymerized to form highly cross-linked, surface degrading polymers is reviewed Typical reaction behavior of multifunctional monomers is discussed, as well as the difficulties associated with photopolymerizing thicker materials and the benefits of temporal control of the photoinitiation process. Characterization of the degradation behavior of thee networks indicates a surface erosion mechanism where the rate of degradation is readily controlled to produce materials that degrade on time scales of days to months. To provide insight into the structural evolution during the polymerization of multifunctional monomers, the degradation products, specifically the kinetic chain lengths, have been analyzed using MALDI-TOF spectroscopy. Additionally, the use of photopolymerizable, degrading polymers for drug delivery is illustrated, and other potential applications of these unique polymers are mentioned.