Two very rare cases of barium boryloxides, the homoleptic [Ba(OB{CH(SiMe3)2}2)2⋅C7H8] and the heteroleptic [{LONO4}BaOB{CH(SiMe3)2}2] stabilised by the multidentate aminoetherphenolate {LONO4}−, are presented, and their structural properties are discussed. The electron-deficient [Ba(OB{CH(SiMe3)2}2)2⋅C7H8] shows, in particular, resilient η6-coordination of the toluene molecule. Together with its amido parents [Ba{N(SiMe3)2}2⋅thf2] and [Ba{N(SiMe3)2}2]2, this complex catalyses the fast and chemoselective dehydrocoupling of borinic acids R2BOH and hydrosilanes HSiR′3, yielding borasiloxanes R2BOSiR′3 in a controlled fashion. The assessment of substrate scope indicates that, for now, the reaction is limited to bulky borinic acids. Kinetic analysis shows that the rate-limiting step of the catalytic manifold traverses a dinuclear transition state. A detailed mechanistic scenario is proposed on the basis of DFT computations, the results of which are fully consistent with experimental data. It consists of a stepwise process with rate-determining nucleophilic attack of a metal-bound O-atom onto the incoming hydrosilane, involving throughout dinuclear catalytically active species.