The synthesis, crystal structures, chemical and spectroscopic properties of NaPdPS 4 , RbPdPS 4 , and RbPdPS 4 {Rb 0 . 3 3 P 0 . 4 S 2 . 2 3 O x } are described. NaPdPS 4 , RbPdPS 4 , are isostructural and crystallize in the tetragonal system I4/mcm with cell parameters a=7.3074(8)A, c=12.2308(14)A and a=8.2954(3)A, c=12.2284(4)A respectively. RbPdPS 4 {Rb 0 . 3 3 P 0 . 4 S 2 . 2 3 O x } is cubic, space group Pm-3n and a=12.0042(2)A. All compounds contain the same 1~[PdPS 4 ] - chains made of alternating square planar Pd 2 + cations and tetrahedral [PS 4 ] 3 - anions. RbPdPS 4 {Rb 0 . 3 3 P 0 . 4 S 2 . 2 3 O x } contains co-crystallized highly disordered molecular species encapsulated within [Rb 8 ] cubic cavities. Spectroscopic solid state 3 1 P NMR, infrared and Raman data as well as elemental analysis suggest that these species could be S n 2 - (n=3 or 4) anions and possibly cationic [P 4 S 6 O] 6 + fragments. NaPdPS 4 and RbPdPS 4 exhibit exfoliative dissolution in polar solvents giving rise to solutions that show signs of complex fluid behavior.