In this study, we utilized the tape-casting method to produce Pb-free (Na0·52K0·4425Li0.0375) (Nb0·8925Sb0·07Ta0.0375)O3 + 2 mol% MnCO3 + y mol% LiF (y = 0 to 3) piezoelectric ceramics. We investigated the impact of LiF sintering in a reduced atmosphere on microstructure, dielectric properties, impedance spectroscopy, and piezoelectric performance. By analyzing the degree of diffuse phase transition, we observed increased density and enhanced long-range order in the sample doped with 1 mol% LiF, which exhibited optimal piezoelectric properties (d33 = 265 pC/N and kp = 0.437) and a minimal diffusion parameter. Moreover, LiF doping enabled sintering at 1020 °C under low PO2, facilitating potential co-firing with Cu inner electrodes to further enhance the piezoelectric performance. Using the optimized parameters, we fabricated a cross-type triaxial piezoelectric accelerometer, demonstrating sensitivities of 2.33, 2.44, and 10.6 mV/g along the X, Y, and Z axes, respectively, with a resonance frequency of ∼2600 Hz and frequency range of ∼1300 Hz. This accelerometer holds promise for vibration measurements in low-frequency mechanical systems.