Microstructure and phase behavior of a semi‐interpenetrating polymer network consisting of 10% poly(ethylene oxide) and 90% crosslinked‐silicone have been studied using various 1H solid‐state NMR methods under fast magic angle spinning in combination with well‐known polymer characterization techniques. Both, 1H double‐quantum MAS NMR spectroscopy as well as NOESY MAS measurements indicate a mixing of the two components on a molecular level.