A novel amorphous Hf-MOFs precursor was successfully synthesized and converted into HfC nanoparticles via one-step pyrolysis. The effects of metal/ligand molar ratios, solvent types, and pyrolysis temperature were systematically studied. High-purity spherical HfC nanoparticles (44.30 ± 9.63 nm) were obtained at 1500 °C using a 1.5:1 metal/ligand molar ratio with mixed anhydrous ethanol/deionized water solvents. At a pyrolysis temperature of 1700 °C, the as-synthesized HfC nanoparticles possessed an exceptionally low oxygen content of 0.76%, alongside a carbon content of 6.42% that almost perfectly matches the theoretical value of stoichiometric HfC. The formation mechanism involving Hf-O-C coordination and carbothermal reduction was clarified. Additive-free HfC ceramics were fabricated using the as-synthesized HfC nanoparticles via spark plasma sintering (1950 °C, 30 MPa, 20 min). The resulting ceramics exhibited a relative density of 96.7% and a Vickers hardness of 20.2 GPa, both of which are significantly superior to those of ceramics sintered from commercial HfC powders under identical conditions (95.8% and 17.8 GPa, respectively). This work provides a promising and feasible pathway for the preparation of other high-quality ultra-high temperature hafnium-based carbide powders and ceramics.