Understanding changes in excited state properties under the influence of an external stimulus, such as pressure or temperature, is important in the context of optimizing molecular components for a number of applications including sensors and imaging reagents. Herein, we use UV/Vis absorption, fluorescence and excitation spectroscopies and fluorescence lifetime measurements supported by calculations to probe the effect of hydrostatic pressure on the excited state characteristics of a conformationally-divergent mechanochromic compound PTZ-DBPHZ (containing two phenothiazine moieties attached to a dibenzo[a,j]phenazine core) in toluene and methylcyclohexane. We demonstrate that hydrostatic pressure can be used to manipulate the equilibria between excited state conformers. This work provides new perspectives for mechanoresponsive materials and as an attractive alternative to conventional ratiometric sensors.[a] Prof.