The reaction of a cyclic alkyl(amino)carbene (CAAC)stabilized thiazaborolo [5,4-d]thiazaborole (TzbTzb) with strong Brønsted acids, such as HCl, HOTf (Tf = O 2 SCF 3 ) and [H(OEt 2 ) 2 ][BAr F 4 ] (Ar F = 3,5-(CF 3 ) 2 C 6 H 3 ), results in the protonation of both TzbTzb nitrogen atoms. In each case X-ray crystallographic data show coordination of the counteranions (Cl À , OTf À , BAr F 4 À ) or solvent molecules (OEt 2 ) to the doubly protonated fused heterocycle via hydrogen-bonding interactions, the strength of which strongly influences the 1 H NMR shift of the NH protons, enabling tuning of both the visible (yellow to red) and fluorescence (green to red) colors of these salts. DFT calculations reveal that the hydrogen bonding of the counteranion or solvent to the protonated nitrogen centers affects the intramolecular TzbTzb-to-CAAC charge transfer character involved in the S 0 !S 1 transition, ultimately enabling fine-tuning of their absorption and emission spectral features.