A stochastic simulation technique was developed to describe the kinetic behavior of bulk multifunctional photopolymerizations and the structural evolution of the polymer networks. Rate equations were written for each of the reacting species. In cross-linking polymerizations, the initiator efficiency, f, and the propagation and termination rate constants, k(p) and k(t), are diffusion-dependent from the onset of the reaction. We were able to calculate f, k(p), and k(t) throughout the simulation using previously developed models. From a waiting time distribution, the time between two consecutive reactions was computed. A specific reaction pathway was chosen from knowledge of the reaction probability density function. Corresponding changes were made in the molecular distribution. With such an approach, we were able to obtain kinetic as well as structural information. The results presented here simulate the bulk polymerization of diethylene glycol diacrylate containing 1% 2,2-dimethoxy-2-phenylacetophenone as the photoinitiator. The simulation was able to predict experimentally observed reaction trends.