The annealing temperature (Ta) dependence of the structural, morphological, electrical and dielectric properties of ZnS thin films was investigated. In this work, we consider the as-deposited and annealed ZnS thin films at different temperatures. The as-deposited films were amorphous in nature. However, the films annealed at Ta ≥ 673 K, exhibited a hexagonal structure with (002) preferential orientation. The post annealing caused an improvement in crystallinity. The best one was observed at Ta = 723 K. Grain size increased from 7 nm to 25 nm as annealing temperature was increased from 673 K to 723 K. The surface of annealed samples is homogenous and uniform and the rms roughness is dependent on the annealing temperature: it increases with temperature within the range 5–50 nm. The film electrical conductance is found to be dependent on frequency measurement and annealing temperature: the dc conductance exhibits semi-conductor behavior for all ZnS films over the explored range of temperature and the conductance was found to enhance with increasing annealing temperature up to 623 K. In addition, it was observed that the highest conductance and lowest activation energy of ZnS films were obtained at an annealing temperature of 623 K. The mechanism of alternating current ac conductance can be reasonably explained in terms of the overlapping-large polaron tunnelling (OLPT) model for samples annealed at 623 K and 673 K. To our knowledge, this conduction mechanism was rarely found in chalcogenide materials. A significant change of Nyquist plot with annealing temperature was noted permitting the correlation between the microstructure and its electrical properties. The impedance analysis investigated that the relaxation process is well pronounced for the both annealed films at 623 K and 673 K. The dielectric behavior was associated to the polarization effect, an improvement on the dielectric constant ε′ and dielectric loss ε′′ with annealing was noticed.