Black crystalline powders of W6PCl17 and W4(PCl)Cl10 were obtained after reducing WCl6 with red phosphorus at 370 and 500 °C. The crystal structures were determined by single-crystal and powder X-ray diffraction analyses. The structure of W6PCl17 is represented by a phosphorus-centered hexanuclear tungsten cluster, whose (W6PCl11)Cl4aCl4/2a–a chains form a hexagonal stick packing structure. The structure of W4(PCl)Cl10 is represented by a Jahn–Teller distorted tetranuclear tungsten cluster that is interconnected into a layered [W4(μ4-PCl)Cl6i]Cl8/2a–a structure containing a chloro-phosphinidene ligand. Solid-state 31P magic-angle spinning (MAS) NMR spectra, electronic structures, and magnetic properties are reported.