Inkjet printing is a newer technology that shows potential for fabricating electronic components embedded in flexible substrates, leading to the development of a new concept of flexible electronics. Conductive polymers are proving to be an almost ideal material for inks because, with certain modifications, they can exhibit the property of intrinsic flexibility along with electrical conductivity. The flexibility and stretchability of conductive polymers can be improved by modifying the conductive backbone with side branches that enable dynamic non-covalent crosslinking through hydrogen bonding. In this work, the conductive polymer poly(3,4-ethylenedioxythiophene) (PEDOT) was used as a backbone onto which acrylate-urethane (AU) side branches were grafted by atom transfer radical polymerization (ATRP) to obtain the graft copolymer PEDOT- g- PAU. The synthesis was carried out in several steps. In the first step, the bromofunctionalized thiophene monomer (ThBr) was synthesized, and in the second step, the ATRP macroinitiator PEDOT-Br. The graft copolymer was synthesized by ATRP polymerization at different durations (0.5 h, 2 h, and 4 h), and the length of the AU side branches was controlled by the length of ATRP synthesis. The obtained samples were characterized by nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM), while the electrochemical properties were investigated by the four-point probe (4PP) method. The obtained graft copolymers were prepared in the form of ink and printed on a flexible polyurethane (PU) substrate using inkjet technology. Subsequently, the electrical conductivity, adhesion of the printed layers and their stretchability were tested. The characterization results confirmed the success of the synthesis of the desired PEDOT-g- PAU graft copolymer, which was then successfully printed on a flexible PU substrate using inkjet technology. The obtained materials exhibit satisfactory electrical and mechanical properties, indicating that the obtained graft copolymer could potentially be used in wearable electronics.