The frequency-dependent complex permittivity spectra (CPS) of the acrylonitrile (ACRN) and 1,4-dioxane (DX) binary mixture in the range from 10 MHz to 30 GHz were measured using the time domain reflectometry (TDR) technique. Experimentally obtained CPS was fitted into the Debye equation. Dielectric relaxation behaviours depend on the temperature and concentration of binary mixtures. The obtained dielectric parameters, the Kirkwood correlation, and the Bruggeman factor have been discussed to understand the molecular association and hydrogen bonding interactions in the mixture.