A series of rubidium rare earth thiophosphates with the formula Rb4Ln2(P2S6)(PS4)2 (Ln = La, Ce, Pr, Nd, Sm, and Gd) were synthesized using the high temperature molten flux crystal growth method utilizing a RbBr flux. Single crystals of all title compounds, as well as phase pure powders of the La-, Ce-, and Sm-containing compositions, were obtained. Single crystals of the title compounds were characterized by single crystal and powder X-ray diffraction for structure and phase identification. Rb4Ln2(P2S6)(PS4)2 crystallizes in the monoclinic crystal system adopting the P21/n space group for the large rare earths (Ln = La, Ce, Pr) and the C2/c space group for the smaller rare earths (Ln = Nd, Sm, Gd). This Rb4Ln2(P2S6)(PS4)2 series is a rare example of thiophosphates containing both tetrahedral [PVS4]3- and dimeric [PIV2S6]4- thiophosphate units that, in this structural family, link corrugated rare earth sulfide chains into sheets. The band gaps of the materials were determined from UV-Vis data and the fluorescence spectrum of Rb4Ce2(P2S6)(PS4)2 was collected. Optical band gaps were estimated to be 2.9 and 2.4 for the Nd and Sm analogues, respectively.