Three new compounds, {U2(H2O)10(O)[Pt(CN)4]3}·4H2O, {Th2(H2O)10(OH)2[Pd(CN)4]3}·8H2O, and {(UO2)2(DMSO)4(OH)2[Ni(CN)4]}, in the actinide tetracyanometallate, Anx[M(CN)4]y, class of compounds have been synthesized and characterized by confocal Raman spectroscopy and single crystal X-ray diffraction. These compounds contain unique structures illustrating dimeric actinide species. The absence of intense charge transfer emission in the visible range for {U2(H2O)10(O)[Pt(CN)4]3}·4H2O, as compared to the platinum starting material, is unusual because of the presence of pseudo-one-dimensional Pt···Pt chains in this compound. Confocal Raman spectroscopy of the cyanide stretching region provides insight into the binding domain (mono-, bi-, tri-, tetradentate) of the tetracyanometallates in these novel structures.