In the present paper, the temperature and salt-dependent dielectric properties of poly(ethylene oxide) (PEO) and poly(vinyl pyrrolidone) (PVP) blend matrix complexed with LiBOB are investigated in the frequency range 1 Hz to 1 MHz and temperature range 40 °C to 100 °C (@10 °C). The real and imaginary part of the complex permittivity, complex conductivity have been simulated in the whole frequency window and the various fitted parameters were evaluated respectively. The estimated value of the dielectric constant and the ac conductivity increases with the increase of temperature. The lowering of relaxation time and hopping length is observed with the salt addition that is in correlation with the complex conductivity results. The modulus formalism was used to analyze the recorded dielectric data. The dc conductivity, hopping frequency, and segmental motion are strongly coupled with each other as evidenced by the Debye-Stoke-Einstein (DSE) plot. An interaction mechanism has also been proposed to explore the effect of temperature on the hopping length, relaxation time, hopping potential barrier and the segmental motion of the polymer chain.