A systematic investigation on the fluorescent spectra of SrB4O7:Sm2+ was performed in detail at high-temperature up to 623 K and/or high pressure up to 23.2 GPa with different pressure-transmitting media (PTMs), respectively. Combined with experiment data of previous research, the change of the 7 D0–5 F0 line (0–0 line) full width at half maximum (FWHM) of SrB4O7:Sm2+ under different pressure environments was specifically discussed. The results indicate that the FWHM of 0–0 line is sensitive to the nonhydrostatic pressure environment in 2-propanol, and methanol and ethanol mixture (ME) PTMs at ambient temperature. The firstorder and the second-order derivation of the temperature dependence of 0–0 line FWHM at ambient pressure are 1.48 (±0.21) × 10−4 nm/K and 9.63(±0.63) × 10−7 nm2 /K2 below 623 K. The 0–0 line FWHM is also sensitive to the non-hydrostatic pressure environment in ME at high-temperature and high pressure simultaneous, the non-hydrostatic transition pressures are 9.6 GPa at 323 K, 11.0 GPa at 373 K, 14.4 GPa at 423 K, respectively. SrB4O7:Sm2+ is recommended as an optical sensor to reflect the change of pressure environment in liquid media at high-temperature and/or high pressure.