A new nitroxide-based biradical having a long electron spin-lattice relaxation time (T-1e) has been developed as an exogenous polarization source for DNP solid-state NMR experiments. The performance of this new biradical is demonstrated on hybrid silica-based mesostructured materials impregnated with 1,1,2,2-tetrachloroethane radical containing solutions, as well as in frozen bulk solutions, yielding DNP enhancement factors (epsilon) of over 100 at a magnetic field of 9.4 T and sample temperatures of similar to 100 K. The effects of radical concentration on the DNP enhancement factors and on the overall sensitivity enhancements (Sigma(dagger)) are reported. The relatively high DNP efficiency of the biradical is attributed to an increased T-1e, which enables more effective saturation of the electron resonance. This new biradical is shown to outperform the polarizing agents used so far in DNP surface-enhanced NMR spectroscopy of materials, yielding a 113-fold increase in overall sensitivity for silicon-29 CPMAS spectra as compared to conventional NMR experiments at room temperature. This results in a reduction in experimental times by a factor >12 700, making the acquisition of C-13 and N-15 one- and two-dimensional NMR spectra at natural isotopic abundance rapid (hours). It has been used here to monitor a series of chemical reactions carried out on the surface functionalities of a hybrid organic-silica material.