High purity phosphorus and phosphorus compounds are prepared by first reacting H.sub.3 PO.sub.4 with a lead compound such as PbO to form Pb.sub.3 (PO.sub.4).sub.2. The Pb.sub.3 (PO.sub.4).sub.2 is reduced with H.sub.2 at a temperature sufficient to form gaseous phosphorus which can be recovered as a high purity phosphorus product. Phosphorus compounds can be easily prepared by reacting the phosphorus product with gaseous reactants. For example, the phosphorus product is reacted with gaseous Cl.sub.2 to form PCl.sub.5. PCl.sub.5 is reduced to PCl.sub.3 by contacting it in the gaseous phase with solid elemental phosphorus. POCl.sub.3 can be prepared by contacting PCl.sub.5 in the gaseous phase with solid P.sub.2 O.sub.5. The general process is particularly suitable for the preparation of radiophosphorus compounds.