Optical pressure measurement technology is based on non-contact monitoring of pressure by observing the luminescent characteristics of luminescent materials under pressure, and has been widely popular. Therefore, the development of luminescent materials with high pressure-sensitivity, high precision, and a wide range of pressure applications has become a key focus. In this paper, the optical pressure sensing performance of a Mn²⁺-based pyroxene-type luminescent material (CaZnGe₂O₆:0.02Mn²⁺) is reported. Within a pressure range of 0.33–9.49 GPa, it demonstrates high sensitivity and excellent cyclic repeatability based on the pressure measurement strategies of both the spectral shift and luminescent intensity ratio. As the pressure increases, the maximum absolute sensitivity (S_a) values (dλ/dP) of the green and red emission positions of Mn²⁺ at different sites in the matrix reach 10.47 nm/GPa and 4.83 nm/GPa, respectively, which are 28.7 and 13.2 times those of the ruby pressure gauge (Al₂O₃:Cr³⁺). Compared with the traditional method that uses a single luminescent peak, this pressure measurement method employing position shift of dual-luminescent emission can enhance the accuracy and reliability of pressure measurement more effectively. In addition, this is the first time that the pressure sensitivity of Mn²⁺-based luminescent materials has been calculated using the ratio of spectral integral intensities in selected areas. The obtained maximum relative pressure sensitivity (S_r) value is 64.28% GPa^–1, and S_r remains above 16.06% GPa^–1 throughout a rather wide pressure range. Undoubtedly, CaZnGe₂O₆:0.02Mn²⁺ exhibits extremely outstanding optical pressure measurement performance, demonstrating its great application potential in the field of optical pressure sensing.