The conductive polyelectrolyte complex poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is ubiquitous in research dealing with organic electronic devices (e.g., solar cells, wearable and implantable sensors, and electrochemical transistors). In many bioelectronic applications, the applicability of commercially available formulations of PEDOT:PSS (e.g., Clevios) is limited by its poor mechanical properties. Additives can be used to increase the compliance but pose a risk of leaching, which can result in device failure and increased toxicity (in biological settings). Thus, to increase the mechanical compliance of PEDOT:PSS without additives, we synthesized a library of intrinsically stretchable block copolymers. In particular, controlled radical polymerization using a reversible addition-fragmentation transfer process was used to generate block copolymers consisting of a block of PSS (of fixed length) appended to varying blocks of poly(poly(ethylene glycol) methyl ether acrylate) (PPEGMEA). These block copolymers (PSS₍₁₎-b-PPEGMEA_(x), where x ranges from 1 to 6) were used as scaffolds for oxidative polymerization of PEDOT. By increasing the lengths of the PPEGMEA segments on the PEDOT:[PSS₍₁₎-b-PPEGMEA_(1-6)] block copolymers, ("Block-1" to "Block-6"), or by blending these copolymers with PEDOT:PSS, the mechanical and electronic properties of the polymer can be tuned. Our results indicate that the polymer with the longest block of PPEGMEA, Block-6, had the highest fracture strain (75%) and lowest elastic modulus (9.7 MPa), though at the expense of conductivity (0.01 S cm^-1). However, blending Block-6 with PEDOT:PSS to compensate for the insulating nature of the PPEGMEA resulted in increased conductivity [2.14 S cm^-1 for Blend-6 (2:1)]. Finally, we showed that Block-6 outperforms a commercial formulation of PEDOT:PSS as a dry electrode for surface electromyography due to its favorable mechanical properties and better adhesion to skin.