Poly(3-methylthiophene) (P3MT) was synthesized directly from indium tin oxide (ITO) electrodes modified with a phosphonic acid initiator, using Kumada catalyst transfer polymerization (KCTP). This work represents the first time that polymer thickness has been controlled in a surface initiated KCTP reaction, highlighting the utility of KCTP in achieving controlled polymerizations. Polymer film thicknesses were regulated by the variation of the solution monomer concentration and ranged from 30 to 265 nm. Electrochemical oxidative doping of these films was used to manipulate their near surface composition and effective work function. Doped states of the P3MT film are maintained even after the sample is removed from solution and potential control confirming the robustness of the films. Such materials with controllable thicknesses and electronic properties have the potential to be useful as interlayer materials for organic electronic applications.