2,2ʹ-Dibromobiphenyl (I) was synthesized in a yield of 78.7% by the reaction of 1,2-dibromobenzene with n-butyllithium in tetrahydrofuran (THF) at - 78°C, achieved using a dry-ice cooling bath. The 5,5-disubstituted-5H-dibenzo[b,d]siloles with R=Et (II), n-Hex (III), or Ph (IV) substituents were synthesized by reacting compound I with n-butyllithium and dichlorodisubstituted silanes having the corresponding substituents in THF. Compounds II and IV were isolated as white solids in yields of 58.9% and 60.6%, respectively, whereas compound III was obtained as a clear liquid in 71.2% yield. The thermal stabilities of compounds I~IV were assessed using thermogravimetric analysis, and their structures were determined using 1H, ¹³C, and ²⁹Si NMR, Fourier-transform infrared, and ultraviolet-visible spectroscopy measurements. The synthesized compounds I~IV match well with the proposed structures in Scheme 1 and were further analyzed using density functional theory calculations. Compounds I~IV exhibited remarkable stability, showing a weight loss of 〈2% the initial weight up to 100°C under a nitrogen atmosphere.