A method for in-site synthesis of transparent conductive coating of poly(3,4-ethylenedioxythiophene)/nano silver hybrid on transparent substrate is provided. Transparent substrate with oxidant coating containing silver salt is immersed into 3,4-ethylenedioxythiophene (EDOT) solution. The oxidant turns EDOT monomer to poly(3,4-ethylenedioxythiophene) (PEDOT) coating on the transparent substrate; meanwhile, the silver salt itself is reduced to nano silver by the EDOT monomer, resulting in a nano silver-doped PEDOT coating. Thereby, a transparent conductive film made of PEDOT/nano silver coating on transparent substrate is obtained. The transparent conductive film with PEDOT/nano silver coating prepared in the present invention possesses the advantages of high electrical conductivity, optical transparency and environmental stability.