Ultrawideline dynamic nuclear polarization (DNP)-enhanced ¹⁹⁵Pt solid-state NMR (SSNMR) spectroscopy and theoretical calculations are used to determine the coordination of atomic Pt species supported within the pores of metal–organic frameworks (MOFs). The ¹⁹⁵Pt SSNMR spectra, with breadths reaching 10 000 ppm, were obtained by combining DNP with broadbanded cross-polarization and CPMG acquisition. Although the DNP enhancements in static samples are lower than those typically observed under magic-angle spinning conditions, the presented measurements would be very challenging using the conventional SSNMR methods. The DNP-enhanced ultrawideline NMR spectra served to separate signals from cis- and trans-coordinated atomic Pt²⁺ species supported on the UiO-66-NH₂ MOF. Additionally, the data revealed a dominance of kinetic effects in the formation of Pt²⁺ complexes and the thermodynamic effects in their reduction to nanoparticles. A single cis-coordinated Pt²⁺ complex was confirmed in MOF-253.