A series of new Hf(IV)-containing fluorides with three different compositions,Cs-2 [M(H2O)(6)][Hf F-2(12)] (M = Ni, Co, Zn), CuHfF6 (H2O)(4), and Cs2Hf3Mn3F20, were synthesized as high-quality single crystals via a mild hydrothermal route. The compounds with compositions of Cs-2 [M(H2O)(6)][Hf F-2(12)] (M = Ni, Co, Zn) and CuHfF6 (H2O)(4 )crystallize in the monoclinic space groups P2(1)/n and P2(1)/c, respectively, while the Cs2Hf3Mn3F20 phase crystallizes in the orthorhombic space group Pmmn. Cs-2 [M-(H2O)(6)][Hf F-2(12)] (M = Ni, Co, Zn) exhibits a complex three-dimensional (3D) crystal structure consisting of edge-sharing dimers of HfF7 polyhedra, which are linked to the divalent metal octahedra via hydrogen bonding. Cs2Hf3Mn3F20 features corner-sharing HfF 7 and MnF7 dimers as well as isolated MnF6 octahedra, while the CuHfF6 (H2O)(4) phase exhibits a 3D structure that consists of HfF6 octahedra linked with neighboring copper octahedral units by hydrogen-bonding interactions. UV-vis spectra of the title compounds were collected and exhibit absorption bands due to electronic transitions in the divalent metal cations (Ni2+, Co2+, Cu2+, and Mn2+). Magnetic susceptibility measurements revealed paramagnetic behavior in the compounds containing the magnetic cations Ni, Co, Cu, and Mn.