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We report on a novel layer by layer (LBL) process for the solution processable thin films, directly on substrates, based on poly(3,4-ethylenedioxythiophene), PEDOT, via in-situ polymerization method. This process allows us to control various critical design parameters such as thickness, polymerization rate and conductivity resulting in the fabrication of good quality thin films of high transparency (93%) and conductivity (850 S/cm). Normalization of transparency (%T) and sheet resistance (SR) of thin films was carried out to calculate a figure of merit (FoM) which is the ratio of electronic conductivity to that of optical conductivity, σ _DC / σ _OP . This ratio for the present LBL method was found out to be approximately 20 which is much higher than the best reported value of 7 for PEDOT thin films prepared by in-situ oxidative polymerization route.