Complex impedance and conductivity were measured for regioregular poly(3-hexylthiophene) (P3HT) at alternating current (AC) voltages using a waveform technique. The waveforms were Fourier transformed from time domain to frequency domain and analyzed at fundamental and higher order harmonic frequencies. It was found that the impedance of the semi-conducting P3HT decreases with increasing electric field strength. The non-linear charge transport is dominated by a third harmonic response that originates from extended polarizability of π-type electronic states. The third order non-linear conductivity can be used to quantify the effect of an electric field on the conduction mechanism and to correlate the intrinsic charge carriers mobility with molecular structure.