A series of low-loss Li3Mg4(Nb1-xVx)O8 (0.02 ≤ x ≤ 0.08) ceramics has been synthesized in this work, with the optimal sintering temperature lowered to 950°C due to the incorporation of V5+ ions. Moreover, the effects of substituting V5+ for Nb5+ on the sintering, composition, structure and properties of the ceramics have been systematically analyzed. It has been discovered that the permittivity (εr) and quality factor (Q×f) of Li3Mg4(Nb1-xVx)O8 ceramics exhibit a correlation with the relative density, which is influenced by the variation in grain size distribution resulting from the substitution of V5+ ions. Additionally, the total lattice energy of Li3Mg4(Nb1-xVx)O8 ceramics is also affected by the bond characteristics within the Nb-O octahedra, thus influencing the Q×f value. The resonant frequency temperature coefficient (τf) fluctuates within a small range. The Li3Mg4(Nb0.98V0.02)O8 ceramics exhibit excellent microwave dielectric properties at 950°C: εr∼14.03, Q×f∼93,425 GHz, τf∼-6.12 ppm/°C, with a relative density reaching 98.3 %. Compared to unsubstituted Li3Mg4NbO8 ceramics, the sintering temperature is reduced by 200°C without forming impurity phases. While adjusting the τf value to nearly zero, it maintains a high Q×f value, indicating promising applications in Low-Temperature Co-fired Ceramics (LTCC).