We describe the synthesis, materials characterization, and dynamic nuclear polarization (DNP) of amorphous and crystalline silicon nanoparticles for use as hyperpolarized magnetic resonance imaging (MRI) agents. The particles were synthesized by means of a metathesis reaction between sodium silicide (Na Si) and silicon tetrachloride (SiCl) and were surface functionalized with a variety of passivating ligands. The synthesis scheme results in particles of diameter ~10 nm with long size-adjusted Si spin-lattice relaxation (T) times (>600 s), which are retained after hyperpolarization by low-temperature DNP.