Polymer electrolyte fuel cells (PEFCs) hold great promise for mitigating the worldwide climate crisis by tapping into the potential of producing clean energy from renewable sources. However, widespread commercial adoption of PEFCs requires addressing the challenges associated with PEFC performance and durability, particularly concerning electrode materials and design. The PEFC electrode is a crucial component of PEFC performance, with the ionomer playing a vital role as both an electrode binder and proton conductor. nano-sized dispersity and high crystallinity of the ionomer are vital properties that are crucial for achieving enhanced performance and durability. However, existing methods for fabricating PEFC electrodes have been unable to attain these desirable ionomer characteristics. In this work, we propose a novel approach to fabricating PEFC electrode architectures with ionomers possessing nano-sized dispersity and high crystallinity using the electrospray deposition (ESD) technique. In the ESD process, a precursor solution is atomized into charged droplets, while evaporating the solvent, and results in the formation of advanced electrode with vertical architecture that exhibits high crystallinity of ionomer, in contrast to much lower crystallinity of those fabricated by conventional decal methods. The ionomer characteristics significantly impact the overall fuel cell performance and durability. Therefore, controlling the residual solvent content during the ESD process is a crucial aspect that is vital for achieving the desired ionomer characteristics. The residual solvent content is tuned by investigating the initial mixed solvent ratio, substrate temperature, and distance between the nozzle to substrate. By fine-tuning the residual solvent content and optimizing the deposition parameters, the ESD technique can overcome the limitations of traditional fabrication methods, resulting in PEFC electrodes that offer enhanced performance, increased durability,