Terahertz time-domain spectroscopy (THz-TDS) has been used to study the temperature-dependent refractive index, absorption coefficient and dielectric constant of polyvinyl chloride/polystyrene (PVC/PS) blends in frequency range of 0.2–1.8 THz. Moreover, the Sellmeier and thermo optic coefficients of PVC/PS blends with different weight ratios have been explored in the temperature range of 25–80 °C. These parameters are used to evaluate the dispersion properties of these blends in the observed frequency range. A clear indication of temperature dependence on the values of refractive index and the real dielectric constant of these blends have been observed. Their values decrease linearly with increasing temperature up to 80 °C. Whereas, no noticeable change has been observed in the imaginary dielectric constant and the absorption coefficient. These results provide a database of temperature-dependent optical and dielectric parameters of PVC/PS polymer blends for their efficient utilization for device fabrication in THz technology.