We propose an optical fiber grating sensor capable of simultaneously measuring pH and temperature based on a phase-shifted long-period fiber grating (PS-LPFG) inscribed on high-birefringence fiber (HBF). The PS-LPFG was fabricated on HBF with CO₂ laser pulses, and a phase shift π was induced by inserting a grating-free fiber region (GFFR) between two identical LPFGs with a grating period of ˜510 μm. The length of the GFFR was set as half of the grating period to induce a π phase shift. With the spectral characteristics of a π-PS-LPFG exhibiting two split attenuation bands, the PS-LPFG written on HBF, which is referred to as the HB-PS-LPFG, can create two polarization-dependent transmission spectra with dual-resonance dips at different wavelengths according to two orthogonal input polarization states, e.g., linear horizontal polarization (LHP) and linear vertical polarization (LVP). For simultaneous measurement of pH and temperature with the fabricated HB-PS-LPFG as a sensor head, the inter-resonance wavelength separation of the dual-resonance dips in each transmission spectrum obtained for an LHP or LVP input signal was exploited as a sensor indicator. By investigating the wavelength changes of the two sensor indicators, which were induced by pH and temperature variations, linear and independent spectral responses to both pH and temperature variations were experimentally confirmed in a pH range from 1 to 11 and a temperature range from 25 to 65 °C. Owing to the unique pH and temperature responses of the fabricated HB-PS-LPFG, ambient variations in pH and temperature could be simultaneously estimated from the measured wavelength changes and sensitivities of the two sensor indicators.