The temperature and pressure dependences of pK for acridine ion ionization were determined up to 200 °C and 2000 bar. The UV-Vis measurements at high temperatures and pressures were conducted in flow-through spectrophotometric cells. Two independent series of experiment were performed: one in a Ti-Pd cell with silica quartz windows for measurements in the ultraviolet region, and another in a Ti grade 5 cell with sapphire windows for use at higher pressures, which permitted measurements in the visible region. Combined chemometric and thermodynamic analyses of the UV-Vis spectrophotometric data were used to extract the ionization constants as well as the changes in molar volume ΔV° for acridine protonation as functions of temperature and pressure. Values of pK decrease from 5.52 to 3.74 with increasing temperature from 25 to 200 °C at saturated water-vapor pressure. The pressure dependence of acridinium ion ionization is small (e.g., pK=5.5 at 25 °C and 2000 bar) and is characterized by positive ΔV°≤1.2cm3⋅mol−1, which is not surprising for this type of isocoulombic reaction involving a large molecul