The doped-bismuth oxide compounds of 7(Bi2O3)-2(WO3), 3(Bi2O3)-(WO3), Bi23V4O44.5 and Bi23P4O44.5 were prepared by the solid state method. Phase composition of these oxides was determined using x-ray diffraction and Raman spectroscopy. Raman spectroscopy showed the 7(Bi2O3)-2(WO3) and 3(Bi2O3)-(WO3), compounds to have similar structures most likely tetragonal. While, Bi23V4O44.5 and Bi23P4O44.5 are reported as belonging to the same triclinic phase, they were observed to have differing spectra and hence structures. Bi23V4O44.5 showed a spectrum with strong bands at 54, 311 and 820 cm(-1) similar to the orthorhombic Bi38Mo7O78 or monoclinic Bi6Mo2O15 phases, whereas, the Bi23P4O44.5 phase has a much simpler spectrum with a strong band at 131 cm(-1). XRD of both the tungsten doped-bismuth oxide compounds showed the same tetragonal structure. With increase in temperature the pattern of the 7(Bi2O3)-2(WO3) system remained constant up to 1123 K, whereas that for 3(Bi2O3)-(WO3) undergoes a transition to a more symmetric structure above 973 K. The XRD patterns of Bi23V4O44.5 and Bi23P4O44.5, show a triclinic pattern, however the Bi23P4O44.5 pattern differs in that there are several extra peaks at d = 2.35849, 2.04542, 1.44252 and 1.43884 Angstrom, likely due to either secondary phase formation or a lowering of symmetry. Both phases are stable to 1123 K, however a few small peaks are observed for the Bi23P4O44.5 compound above 973 K.