The study meticulously examined the impact of varying sintering temperatures on the phase transformations, crystallographic configurations, dielectric response mechanisms, and lattice vibrational characteristics of the ZnWO4 ceramics. Far-infrared reflectance spectra were fitted using a four-parameter semiquantum model to obtain the intrinsic dielectric properties. Moreover, the contribution to the dielectric properties for each vibrational mode was analyzed, indicating that the lower-frequency mode had the most contribution. The relationship linking the structural aspects to the properties of ZnWO4 ceramics was elucidated through an analysis of the Raman spectral modes across a range of sintering temperatures, overcoming the limitation of solely textual description without mathematical quantification. When sintered at 1070 °C, the ZnWO4 ceramic had the best dielectric properties: εr = 14.81, Q×f = 34,239 GHz (f = 9.69 GHz), with the highest relative density of 96.95 %.