Complex permittivity spectra of binary mixtures of varying concentrations of -picoline and Methanol (MeOH) have been obtained using time domain reflectometry (TDR) technique over frequency range 10 MHz to 25 GHz at 283.15, 288.15, 293.15 and 298.15 K temperatures. The dielectric relaxation parameters namely static permittivity (" 0 ), high frequency limit permittivity (" 11 ) and the relaxation time () were determined by fitting complex permittivity data to the single Debye/Cole-Davidson model. Complex nonlinear least square (CNLS) fitting procedure was carried out using LEVMW software. The excess permittivity (" E 0 ) and the excess inverse relaxation time (1/Þ E which contain information regarding molecular structure and interaction between polar-polar liquids were also determined. From the experimental data, parameters such as effective Kirkwood correlation factor (g eff ), Bruggeman factor (f B ) and some thermo dynamical parameters have been calculated. Excess parameters were fitted to the Redlich-Kister polynomial equation. The values of static permittivity and relaxation time increase nonlinearly with increase in the mol-fraction of MeOH at all temperatures. The values of excess static permittivity (" 0 E ) and the excess inverse relaxation time (1/Þ E are negative for the studied -picoline -MeOH system at all temperatures.