The relationship between observed swelling of two cross-linked polystyrene resins and the microenvironment within polymer matrixes has been examined. Polystyrene cross-linked with either divinyl benzene (Merrifield resin) or 1,4-bis(4-vinylphenoxy)butane (JandaJel) was investigated with fluorescence and electron-paramagnetic resonance spectroscopy. Fluorescence spectroscopy revealed a superior correlation between observed swelling and solvation effects using a dansyl probe with JandaJel than with Merrifield resin. However, the internal viscosity of pre-swollen JandaJel is higher than Merrifield resin, as determined by EPR measurements. The combination of these two analytical methods provides insights into the physical differences observed between these two chemically similar resins and suggests caution should be used if using singular physical techniques to probe the microenvironment of polymeric matrixes.