The first quaternary plutonium metal thiophosphates have been synthesized by the reactive flux method and characterized by single-crystal X-ray diffraction: K(3)Pu(PS(4))(2) (I), KPuP(2)S(7) (II), RbPuP(2)S(7) (III), and CsPuP(2)S(7) (IV). All four compounds crystallize in the monoclinic space group P2(1)/c with Z = 4. Compound I has cell parameters of a = 9.157(1) A, b = 16.866(2) A, c = 9.538(1), and beta = 90.610(3)degrees. Compound II has cell parameters of a = 9.641(1) A, b = 12.255(1) A, c = 9.015(1) A, and beta = 90.218(1)degrees. Compound III has cell parameters of a = 9.8011(6) A, b = 12.3977(7) A, c = 9.0263(5) A, and beta = 90.564(1)degrees. Compound IV has cell parameters of a = 10.1034(7) A, b = 12.5412(9) A, c = 9.0306(6) A, and beta = 91.007(1)degrees. Compound I is isostructural to a family of rare-earth metal thiophosphates and comprises bicapped trigonal prismatic PuS(8) polyhedra linked in chains through edge-sharing interactions and through thiophosphate tetrahedra. Compounds II-IV crystallize in a known structure type not related to any previously observed actinide thiophosphates and contain the (P(2)S(7))(4-) corner-shared bitetrahedral ligand as a structural building block. A summary of important bond distances and angles for these new plutonium thiophosphate materials is compared to the limited literature on plutonium solid-state compounds. Diffuse reflectance spectra confirm the Pu(III) oxidation state and Raman spectroscopy confirms the tetrahedral PS(4)(3-) building block in all structures.