Room-temperature photolysis of the aminoboryl complex [(OC)(5)Cr═B═N(SiMe(3))(2)] in the presence of a series of mono- or bis(boryl) alkynes bis{bis(dimethylamino)boryl}ethyne, 1-phenyl-2-bis(dimethylamino)borylethyne, and 1-trimethylsilyl-2-bis(dimethylamino)borylethyne led to the isolation of hitherto unknown borylborirenes in resonable yields, that is, [(RC═CR')(μ-BN(SiMe(3))(2))] (7, R = B(NMe(2))(2), R' = Ph; 8, R = R' = B(NMe(2))(2); 9, R = B(NMe(2))(2), R' = SiMe(3)). The borirenes were isolated and spectroscopically characterized by multinuclear NMR, IR, and UV/vis spectroscopy, crystallography, and elemental analysis. Reactivity studies of the borirenes demonstrated their behavior toward different Lewis bases. The isolated adducts and the parent borirenes were compared to 1,3-mesityl-2-phenylborirene and its adducts. To gain insight into the electronic structure and to evaluate the influence of the exocyclic groups, Density Functional Theory (DFT) calculations were carried out.