Borenium ions, originally synthesized as fundamentally important laboratory curiosities, have attracted significant attention due to their applications in catalysis and frustrated Lewis pair chemistry. However, investigations of the materials properties of these types of compounds are exceptionally rare. Herein, we report the synthesis, molecular structures, and optical properties of a new class of air-stable borenium ions, stabilized by the strongly donating carbodicarbene (CDC) ligand (<b>2</b>, <b>3</b>, <b>6</b>). Notably, CDC-borafluorenium ions exhibit thermoluminescence in solution, a result of a twisted intramolecular charge transfer process. The temperature responsiveness, which is observable by the naked eye, is assessed over a 20 to -60 °C range. Significantly, compound <b>2</b> emits white light at lower temperatures. In the solid state, these borocations exhibit increased quantum yields due to aggregation-induced emission. CDC-borafluorenium ions with two different counteranions (Br<sup>-</sup>, BPh<sub>4</sub><sup>-</sup>) were investigated to evaluate the effect of anion size on the solution and solid-state optical properties. In addition, CDCs containing both symmetrical and unsymmetrical N-heterocycles (bis(1-isopropyl-3-methylbenzimidazol-2-ylidene)methane and bis(1,3-dimethyl-1,3-dihydro-2<i>H</i>-benzo[<i>d</i>]imidazol-2-ylidene)methane) were tested to understand the implications of free rotation about the CDC ligand carbon-carbon bonds. The experimental work is complemented by a comprehensive theoretical analysis of the excited-state dynamics.