Four new rubidium thorium molybdates have been synthesized by high-temperature solid-state reactions. The crystal structures of Rb8Th(MoO4)(6), Rb2Th(MoO4)(3), Rb4Th(MoO4)(4), and Rb4Th5(MoO4)(12) were determined using single-crystal X-ray diffraction. All these compounds construct from MoO4 tetrahedra and ThO8 square antiprisms. The studied compounds adopt the whole range of possible structure dimensionalities from zero-dimensional (0D) to three-dimensional (3D): finite clusters, chains, sheets, and frameworks. Rb8Th(MoO4)(6) crystallizes in OD containing clusters of [Th(MoO4)(6)](8-). The crystal structure of Rb2Th(MoO4)(3) is based upon one-dimensional chains with configuration units of [Th(MoO4)(3)](2-). Two-dimensional sheets occur in compound Rb4Th(MoO4)(4), and a 3D framework with channels formed by thorium and molybdate polyhedra has been observed in Rb4Th5(MoO4)(12). The Raman and IR spectroscopic properties of these compounds are reported. Temperature-depended phase transition effects were observed in Rb2Th(MoO4)(3) and Rb4Th(MoO4)(4) using thermogravimetry-differential scanning calorimetry analysis and high-temperature powder diffraction methods.