Although the activation of elemental sulfur by main group compounds is well-documented in the literature, the products of such reactions are often heterocyclic in nature. However, the isolation and characterization of sulfur catenates (i.e., acyclic sulfur chains) is significantly less common. In this study, we report the activation of elemental sulfur by the 9-CAAC-9-borafluorene radical (1) and anion (2) (CAAC = (2,6-diisopropylphenyl)-4,4-diethyl-2,2-dimethyl-pyrrolidin-5-ylidene) to form boron–sulfur catenates (3–6). From the isolation of the octasulfide-bridged compound 3, a sulfur extrusion reaction using 1,3,4,5-tetramethylimidazol-2-ylidene (IMe₄) was used to decrease the sulfide chain length from eight to seven (4). Bonding analysis of compounds 3–6 was performed using density functional theory, which elucidated the nature of the sulfur−sulfur bonding observed within these compounds. We also report the synthesis of a series of borafluorene-chalcogenide species (7–9), via diphenyl dichalcogenide activation, which portray characteristics described by an internal heavy atom effect. Compounds 7–9 each exhibit blue fluorescence, with the lowest energy emissive process (S₂ → S₀) at 436 nm (7 and 8) and 431 nm (9). The S₁ → S₀ emission is not observed experimentally due to a Laporte forbidden transition. Density functional theory was employed to investigate the frontier molecular orbitals and absorption and emission profiles of compounds 7–9.