tert-Butylphosphonic acid and rare-earth precursors are employed to construct four trinuclear rare-earth phosphonate clusters, RE3( tBuPO3)2(hfac)5(CH3OH)8]·2CH3OH (RE = Eu, Y, Pr, and Sm; hfac = hexafluoroacetylacetonate), which are composed of three RE3+ ions alternately bridged by two phosphonates. With the introduction of bismuth oxido diketonate, [Bi9O7(hfac)13], three different types of rare-earth/bismuth phosphonate clusters, Bi12RE2 (RE = Pr and Sm), Bi6Eu7, and Bi6Y9, are successfully obtained via variation of the reaction conditions, and they are the first reported examples of bismuth-oxo clusters encapsulated by cyclic rare-earth-oxo or rare-earth/bismuth-oxo phosphonate clusters, respectively. These clusters show obvious absorption in the UV region, and the Eu-containing clusters exhibit bright-red fluorescence.