The versatile cross-linking chemistry of poly(dimethylsiloxane) (PDMS)-based materials affords a large research space in which polymers with widely varying elastomeric properties may be synthesized. Parameters such as chain length, cross-link density, cross-link functionality, filler content, and chain chemistry can all be modified to produce materials with specific physical and mechanical properties. Commercial polysiloxane-based, "silicone" elastomers are generally intractable, which makes the precise characterization of their networks problematic. We report here the application of equilibrium solvent uptake analysis and H-1 double quantum nuclear magnetic resonance (H-1 DQ NMR) spectroscopy to determine the network topology of end-linked PDMS networks with nonideal network topology. Despite their structural complexity, we can quantify both the classical and nonclassical contributions to network structure using H-1 DQNMR which are in reasonable agreement with solvent uptake data. These findings serve as the foundation for future investigations of even more complex commercial silicones using H-1 DQ NMR.