To overcome the limitation of low sensitivity in optical pressure sensors, Ce3+-doped NaMgBO3 phosphors have been synthesized via high-temperature solid-phase method. Density functional theory (DFT) calculations and absorption spectroscopy analysis demonstrate that the NaMgBO3 crystal structure serves as an excellent host material for rare-earth ions luminescence. Upon 375 nm excitation, bright cyan emission from Ce3+ was observed. To assess the potential application in optical pressure sensing, the pressure-dependent photoluminescence spectra and Raman spectra of the NaMgBO3:0.01Ce3+ sample were measured and analyzed in detail. As pressure increased from 0.31 to 17.18 GPa, the emission peaks shift from 469.3 to 496.1 nm, accompanied by a visible color transition from cyan to green, achieving the maximum sensitivity of 2.94 nm/GPa. Furthermore, quantitative evaluation of pressure sensitivity using chromaticity coordinates yields a maximum sensitivity of 6.22 % GPa−1. These results demonstrate that Ce3+-doped NaMgBO3 phosphors exhibit potential for optical manometry applications, where pressure-induced chromaticity shifts and spectral displacements enable dual-mode detection, thereby achieving high-precision pressure measurements across a broad operational range.