Two types of solid-state F-19 NMR spectroscopy experiments are used to characterize phase-separated hyperbranched fluoropolymer-poly(ethylene glycol) (HBFP-PEG) crosslinked networks. Mobile (soft) domains are detected in the HBFP phase by a rotor-synchronized Hahn echo under magic-angel spinning conditions, and rigid (hard) domains by a solid echo with no magic-angel spinning. The mobility of chains is detected in the PEG phase by H-1 -> C-13 cross-polarization transfers with H-1 spin-lock filters with and without magic-angle spinning. The interface between HBFP and PEG phases is detected by a third experiment, which utilized a F-19 -> H-1-(spin diffusion)-H-1 -> C-13 double transfer with C-13 solid-echo detection. The results of these experiments show that composition-dependent PEG inclusions in the HBFP glass rigidify on hydration, consistent with an increase in macroscopic tensile strength.