Designing guidelines for glass-free low-temperature cofired ceramic (LTCC) materials were proposed from the point of view of crystal chemistry. As an example, Ca1-x(Nd0.5Li0.5)xWO4 was successfully designed as glass-free LTCC materials by crystal chemistry. The sintering behavior, microstructure, and microwave dielectric properties of Ca1-x(Nd0.5Li0.5)xWO4 ceramics were investigated in this study. The structure and microstructure of the compounds were investigated by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). The microwave dielectric properties of the ceramics were studied with a network analyzer at the frequency of about 913 similar to GHz. Continuous solid solutions Ca1-x(La0.5Na0.5)xWO4 (0.1 similar to=similar to x=0.5) were formed as expected in the experimented composition range. They could be sintered into dense ceramics (approximately 96%98% theoretical density) at 825 degrees C875 degrees C per 2 similar to h. All samples exhibit Scheelite structure (I41/a) phase. Both of the sintering temperature and microwave dielectric properties, especially the temperature coefficient of resonant frequency (tf), could be tuned in a wide range. Combined excellent microwave dielectric properties with er similar to=similar to 11.7, Q similar to x similar to f similar to=similar to 36 similar to 700 similar to GHz, and tf similar to= 5.36 similar to ppm/degrees C could be obtained for the x similar to=similar to 0.2 composition after sintering at 825 degrees C/2 similar to h. The chemical compatibility of Ca0.8(Nd0.5Li0.5)0.2WO4 ceramic with silver (Ag) powders was also investigated. No chemical reaction has taken place between the matrix phase and Ag after sintering at 850 degrees C/2 similar to h. Thus, it can be used as a promising glass-free microwave dielectric material for LTCC applications.