Innovations in industrial automation, information and communication technology, renewable energy sources, and sensor development have been paving the way for smart devices capable of collecting and transmitting information to the Internet for some time now. Given the increasing demand for large yet cost-effective forms of such devices, printed electronics has been attracting the attention of both industry and academia. Inkjet printing offers a straightforward method for manufacturing the next generation of electronic devices by combining the design freedom of additive manufacturing technologies with the tunable properties of functional materials and their potential integration into new structures. Conductive polymers stand out in this context due to their diverse properties, such as corrosion resistance, electrical conductivity, and low density. One of the main representatives of conductive polymers is poly(3,4-ethylenedioxythiophene) (PEDOT), known for its biocompatibility, chemical stability, and electrical conductivity, which classifies it as a semiconductor. Despite its excellent properties, PEDOT lacks stretchable and self-healing characteristics, limiting its application in wearable electronics that come into contact with human skin. Therefore, the aim of this work is to synthesize the graft copolymer PEDOT-g-HEMA-PCL with two different molecular weights of HEMA-PCL. The synthesis was conducted in four steps: the first step was the synthesis of the monomer 2-(thiophen-3-yl) ethyl 2-bromo-2-methylpropanoate (ThBr), followed by the synthesis of the macroinitiator PEDOT-Br in two ratios, 2:1 and 5:1. The third step involved the synthesis of the graft copolymers PEDOT-g-HEMA-PCL, consisting of two HEMA-PCL with different molar masses, via atom transfer radical polymerization (ATRP). The obtained samples were characterized by nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). Additionally, inks were prepared for inkjet printing on a polyurethane (PU) substrate, their electrical conductivity was tested using the four-point probe method, their stretchability and adhesion properties were also tested.