We report remarkably high, up to 100-fold, signal enhancements in 19 F dynamic nuclear polarization (DNP) magic angle spinning (MAS) spectra at 14.1 T on HIV-1 CA capsid protein assemblies. These enhancements correspond to absolute sensitivity ratios of 12-29 and are of similar magnitude as seen for 1 H signals in the same samples. At MAS frequencies above 20 kHz, it was possible to record 2D 19 F-13 C HETCOR spectra, which contain long-range intra-and intermolecular correlations. Such correlations provide unique distance restraints, inaccessible in conventional experiments without DNP for protein structure determination. Furthermore, systematic quantification of the DNP enhancements as a function of biradical concentration, MAS frequency, temperature, and microwave power is reported. Our work establishes the power of DNP-enhanced 19 F MAS NMR spectroscopy for structural characterization of HIV-1 CA assemblies and this approach is anticipated to be applicable to a wide range of large biomolecular systems.