As one of the candidates of low-temperature cofired ceramics (LTCC), the sintering behavior, dielectric properties, and silver chemical compatibility of NaCaVO4 were studied. The bulk ceramic samples were densified well at a low sintering temperature of 720 oC with an optimal bulk density of 2.87 g/cm3. Excellent microwave dielectric properties with a low relative permittivity εr ~ 9.9, a high quality factor Q × f ~ 31,600 GHz, and a temperature coefficient of resonance frequency τf ~ -66.5 ppm/°C were achieved at 11.5 GHz. The far infrared reflectivity spectra revealed the intrinsic dielectric properties (relative permittivity of 8.34 and dielectric loss of 2.7×10-4) are comparable to the measured values. The absence of chemical reaction between NaCaVO4 and silver at firing temperature, evidenced by X-ray diffraction and energy dispersive spectroscopy indicated the potential prospect for LTCC application. Furthermore, the very low density of NaCaVO4 opens up an avenue for its potential applications in light-weight devices.