Using the Time Domain Reflectometry (TDR), dielectric relaxation studies were carried out on polystyrene-with substituted phenols p-cresol, m-cresol and o-cresol mixture in different non-polar solvents CCl 4, benzene and 1, 4- dioxane for various concentrations over the frequency range from 10 MHz-20 GHz at 303K. The dielectric parameters such as static dielectric constant ε 0), relaxation time (τ) were found and discussed to yield information on the molecular interaction of the system. The dielectric constant and relaxation time were increased with the increase of wt % of polystyrene were noticed. The FTIR analysis was supporting the dielectric results. The intermolecular interaction has been discussed using the excess parameters like excess permittivity (ε E) and excess inverse relaxation time (1/τ) E.