Borylenes, RB, are elusive reactive intermediates. Still not much is known about their excited states from spectroscopic experiments, and existing knowledge is limited to diatomic borylenes only. The electronic structure and geometry of borylenes with diverse substituents on boron (where R = H, F, Cl, CH3, CF3, tBu, NH2, Ph, and SiMe3) were studied by means of computational chemistry. For this purpose, geometries of borylenes in their lowest singlet and triplet states were optimized at the B3LYP/def2-TZVP level of theory. Additionally, the influence of substitution on the energies of frontier molecular orbitals, HOMO-LUMO energy gaps, singlet-triplet energy splittings, and excitation energies was investigated. Two lowest vertical singlet-singlet excitations were computed using EOM-CCSD and TD-DFT (using hybrid B3LYP, and long-range separated CAM-B3LYP and ωB97X functionals) in combination with the aug-cc-pVTZ basis set. The electronic transitions involve excitations from nonbonding sp boron orbital (HOMO) mainly to empty p(B) orbitals and partially to the orbitals of the substituent, and are of n → π* type. The results can facilitate prospective identification of borylenes, e.g., in UV-vis matrix isolation or time-resolved spectroscopy experiments.