Reactions of 9-carbene-9-borafluorene monoanion (1) with elemental selenium and selenium-containing reagents are reported. When compound 1 is reacted with grey selenium in THF, various boryl-substituted selenides and diselenides are produced (2–6), including molecules resulting from migration of the carbene ligand Dipp group (Dipp = 2,6-diisopropylphenyl). However, when a similar reaction between 1 and grey selenium is performed in toluene in the presence of 18-crown-6, boryl-substituted selenide 7 is obtained as the sole boron-containing product. As compound 7 is the monomeric variant of organoselenide 3, 18-crown-6 promotes both product selectivity and solubility in a nonpolar solvent. Diselenide 5, which features a trans-bent B–Se–Se–B core, was directly isolated via reaction of 1 with Se₂Cl₂ in THF. Computational modeling suggests that the formation of 5 proceeds via a radical mechanism. This was supported by an experiment demonstrating that the CAAC-borafluorene radical also reacts with SeCl₂ to yield 5 [CAAC = (2,6-diisopropylphenyl)-4,4-diethyl-2,2-dimethyl-pyrrolidin-5-ylidene]. Energy decomposition analysis of 5 indicates a covalent borafluorene–diselenide bond (ΔE_int, −168.9 kcal mol^–1). All of the new compounds were fully characterized via single-crystal X-ray diffraction and multinuclear nuclear magnetic resonance (¹H, ¹³C, ¹¹B, and ⁷⁷Se).