Tri-p-tolylbismuth perchlorate (1) and μ-oxo-bis[(perchlorato)tri-p-tolylbismuth] (2) have been synthesized by the reaction between tri-p-tolylbismuth dibromide and silver perchlorate and its hydrate. The complexes have been studied by chemical analysis, IR spectroscopy, and X-ray diffraction. Complex 1 is triclinic, space group Pī, Z = 4, a =10.7271(9) A, b = 13.5585(11) A, c = 18.1592(13) A, α = 110.867(3)°, β = 94.944(3)°, γ = 96.888(3)°, V = 2426.3(3) A3, ρcalcd = 1.865 g/cm3; complex 2 crystallizes in trigonal symmetry, space group R $$\bar 3$$ , a = 13.1157(2) A, c = 22.1959(2) A, γ = 120°, V = 3306.64(8) A3, ρcalcd = 1.777 g/cm3. The bismuth atoms in the molecular structure of complex 1 have a distorted trigonal bipyramidal coordination to the apically arranged oxygen atoms of perchlorate ions (Bi–C, 2.180(5)–2.201(5) A; Bi–O, 2.324(4)–2.355(4) A; OBiO axial angles, 170.1(1)°, 174.5(1)°). The structure of complex 2 contains binuclear [p-Tol3Bi(ClO4)]2O molecules (Bi–O, 2.371(15), 1.9107(7) A; OBiO axial angle, 180.0°).