Solvothermal reactions of TaCl5 with LiNH2 or Mg3N2 lead to amorphous products at temperatures up to 500 °C. Post-reaction annealing under nitrogen yields crystalline products with Ta3N5 (LiNH2) and TaN (Mg3N2) structures. When these reactions are carried out with LiNH2 in refluxing mesitylene, rods of Ta3N5-structured material are obtained. Using commercial LiNH2 these have dimensions of 5 × 200 nm but are contaminated with LiTaO3. With high purity LiNH2 a black oxide-free but carbon-containing material presents as rods of 20–50 nm length. Higher temperature reactions in an autoclave lead to isotropic nanocrystals of ca. 10 nm diameter of a nitrogen-deficient or carbide-substituted Ta3N5-type material. Carbon incorporation is attributed to solvent decomposition at the temperatures required for the reactions. The TaN derived from reactions with Mg3N2 consists of nanoparticles of 6–8 nm in diameter.