Triboluminescence (TL) of the methyltriphenylphosphonium tetrahalomanganate(II) complexes such as bis(methyltriphenylphosphonium) tetrabromomanganate (PMBB) and bis(methyltriphenylphosphonium) dibromodichloromanganate (PMBC) was switched ON and OFF reversibly by vapors of aprotic and protic solvents, respectively, for the first time. Detailed analyses indicate that solids of the PMBB and the PMBC undergo phase transitions depending on the environment, which regulate the TL activity of these compounds. The combined results of luminescence, powder X-ray diffraction, differential scanning calorimetry, and electron paramagnetic resonance were used to demonstrate crystal dynamism as well as the TL emission of PMBB and PMBC.