Metal nitrides are intensely investigated because they can offer high melting points, excellent corrosion resistance, high hardness, electronic and magnetic properties superior to the corresponding metals/metal oxides. Thus, they are used in diverse applications including refractory materials, semiconductors, electronic devices, and energy storage/conversion systems. Here, we present a simple, novel, scalable and general route to metal nitride precursors by reactions of metal chlorides with hexamethyldisilazane [HMDS, (Me 3 Si) 2 NH] in tetrahydrofuran or acetonitrile at low temperatures (ambient to 60 • C/N 2 ). Such reactions have received scant attention in the literature. The work reported here focuses primarily on the Al-HMDS precursor produced from the reaction of AlCl 3 with HMDS (mole ratio = 1:3) characterized by matrix-assisted laser desorption/ionization-time of flight, Fourier-transform infrared spectroscopy, thermogravimetric analysis-differential thermal analysis, and multinuclear nuclear magnetic resonance spectroscopy (NMRs) for chemical and structural analyses. The Al-HMDS precursor heated to 1600 • C/4 h/N 2 produces aluminum nitride, characterized by X-ray powder diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy/energy-dispersive Xray spectroscopy, and magic-angle spinning NMR. On heating to 800-1200 • C/4 h/N 2 , the precursor transforms to an amorphous, oxygen-sensitive powder with very high surface areas (>200 m 2 /g) indicating nanosized particles, which can be used as additives to polymer matrices to modify their thermal stabilities. Al 2 O 3 is also presented in the final product after heating, due to its high susceptibility to oxidation. This approach was extended via proof-of-concept studies to other metal chloride systems, including Zn-HMDS, Cu-HMDS, Fe-HMDS, and Bi-HMDS. The formed precursors are volatile, offering the potential utility as gas-phase deposition precursors for their corresponding metal nitrides.