Monodisperse porous particles of poly(divinylbenzene) prepared by the activated swelling method have been investigated by solid-state C-13 crosspolarization magic-angle spinning (CPMAS) nuclear magnetic resonance (NMR) relaxation measurements. Homopolymeric combinations of two porogens (toluene and 2-ethylhexanoic acid) and two monomers (meta- and para-divinylbenzene) were studied. Residual vinyl groups were systematically reacted with increasing amounts of bromine, producing 20 different polymers samples for which we measured crosspolarization times, T-CH, proton rotating frame spin-lattice relaxation, T-1 rho(H), C-13 spin-lattice relaxation, T-1(C), and proton spin-lattice relaxation, T-1(H). These parameters were chosen to reflect expected changes in a wide range of frequencies of motion as a function of structure. Relative differences in the molecular mobility of the major functional groups (aromatic, vinyl and aliphatic) is related to initial reactants used, vinyl concentration, relative reactivity of vinyl groups, distribution of vinyl groups, pore structure, and degree of crosslinking. Variable temperature H-1 combined rotation and multiple pulse NMR (CRAMPS) was used to derive activation energies for selected samples via measurement of the proton spin-lattice relaxation time, T-1(H). Irreversible thermal effects were observed in ambient temperature relaxation after heating to temperatures in the range of 393-418 K. Simple univariate statistical analyses failed to reveal consistent correlations among the known variables. However, the application of more sophisticated multivariate and neural network analyses allowed excellent structure-property predictions to be made from the relaxation time data.