Electrochemical characteristics of poly‐3‐methylthiophene have been investigated in liquid electrolyte. This polymer was electropolymerized on smooth platinum rods and cycled between 2.0 and 4.0V relative to lithium. The polymer showed a 2.57V reduction wave (due to reduction) and oxidation at 3.55V. Use of poly‐3‐methylthiophene as a cathode substrate during discharge is therefore of interest to rechargeable cell technology since it readily reduces on its surface and allows discharge products to become oxidized at low charging potentials.