The alkoxide Bi[OCMe2(2-C4H3S)]3 (1) is formed by the reaction of three equiv. of the alcohol HOCMe2(2-C4H3S) with Bi(OtBu)3 and subsequent hydrolysis provides the bismuth oxido cluster [Bi4O2{OCMe2(2-C4H3S)}8] (2). In contrast, the reaction of Bi(OtBu)3 and Bi[N(SiMe3)2]3 with the silanols HOSiMe2(2-C4H3X) (X = O, S, Se, and NMe), HOSiMe2(2-C4H2S-5-SiMe3) and HOSiMe2(3-C4H3S) leads to the formation of tris(heteroaryl)bismuthines Bi(2-C4H2X-5-R)3 [where X = O, R = H (3); X = S, R = H (4); X = S, R = SiMe3 (5); X = NMe, R = H (6); X = Se, R = H (7)] and Bi(3-C4H3S)3 (8). For the silanols, bismuth-carbon bond formation is observed rather than silanol-alcoholate or silanol-amide exchange. The structures of compounds 1, 2, and 4-7a in the solid state were established by single crystal X-ray diffraction and all compounds except 5 show London dispersion type bismuthπ heteroarene interactions. For the bismuthine Bi(2-C4H3Se)3 (7), two polymorphs were isolated depending on the conditions of crystallization. At 8 °C, polymorph I (7a) crystallizes from an n-hexane solution in the triclinic space group P1[combining macron], whereas polymorph II (7b) crystallizes at 20 °C from a CH2Cl2/n-pentane solution in the monoclinic space group P21/c. The heteroaryl bismuthines 3 and 4 exhibit 2D network structures as a result of bismuthπ heteroarene interactions, whereas for the pyrrole derivative 6 the dispersion type interactions provide separated dimers.