In this paper, the evolution of the microstructure for the zinc silicate ceramics with different Zn/Si ratios was revealed, and the factors influencing their dielectric properties were discussed. Our results demonstrate that Zn volatilization plays an important role on the defect structure of the samples. Low relative density, high conductivity loss caused by volatilization, and the presence of ZnO phase collectively result in low quality factor (Qf) of Zn2.0SiO4.0. By using the powder embedded sintering method, the loss could be reduced owing to the suppression of volatilization. As the Zn/Si ratio decreases, the ZnO disappears, while the Si-rich phase emerges and increases. The formation of a liquid phase results in a dense microstructure of the non-stoichiometric samples. Moreover, these samples exhibit a minor degree of Zn loss, probably because the presence of liquid phase constraints the volatilization during sintering. The samples with x = 1.8 display desirable properties, including a relative dielectric constant (εr) of 6.5, a Qf of 100,800 GHz, and a temperature coefficient of resonant frequency (τf) of −21.3 ppm/°C, due to their high degree of densification, slight zinc loss, and the elimination of the ZnO phase.