To facilitate the characterization of polymer networks, a comparison was made between branching theory and Monte Carlo simulations using an amine-cured epoxy as an example for step-growth polymer networks. The primary objective was the validation of the simulation results with the existing statistical theories by a crosscheck, to ensure that simulations can also be used for the characterization of real, highly complicated multicomponent systems, which are intractable by theories. Commercially available software was used for simulation; the theoretical calculations were performed using the approach of Macosko and Miller. In general, the results of both methods are consistent; the simulation revealed some uncertainties only in the vicinity of the gel point. Since the statistical theories have been validated experimentally, it may be concluded that the simulation can also successfully be used for the treatment of real, highly complicated multicomponent systems, which for practical purposes are intractable by statistical theories.