This paper reports study of Raman and Photoluminescence (PL) characteristics of ZnTe crystal excited by near band-edge laser. The Raman spectra exhibited strong longitudinal-optical (LO) multiphonon peaks due to onset of resonance phenomenon. The optical excitation power response showed increase in the Raman multiphonon peak intensity with laser power with no shift in peak positions. The PL spectra also exhibited similar effect with the near band-edge peak intensity increasing with laser power without any peak shift. Increasing the temperature from 80 to 300 K showed a decrease in the multiphonon peak intensity. The Raman spectra at different sample temperatures are dominated by strong LO multiphonon peaks; however, a transverse optical (TO) Raman peak was also observed in the Raman spectra at temperature of 173 K and below indicating a shift from resonance (at room temperature and down to 173 K) to non-resonance condition (below 173 K). In addition, strong electron–phonon coupling is observed in the bulk ZnTe single crystal substantiated by high values of Huang–Rhys parameter in the considered temperature range. Within the band-edge resolvable temperature range (300–223 K), the near band-edge luminescence intensity also increased with decrease in the sample temperature along with a blue shift in the peak position.