Sustainable and scalable fabrication of electrode materials with high energy and power densities is paramount for the development of future electrochemical energy storage devices. The electrode material of a supercapacitor should have high electrical conductivity, good thermal and chemical stability, and a high surface area per unit volume (or per unit mass). Researchers have made great efforts to use two-dimensional (2D) nanomaterials, but the separated 2D plates are re-stacked during processing for electrode fabrication, impeding the transport of ions and reducing the number of active sites. We developed a novel process for manufacturing thin and flexible electrodes using a 2D material (MXene,Ti3AlC2) and a conducting polymer (poly(3,4-ethylenedioxythiophene), PEDOT). Because the PEDOT layer is electrochemically synthesized, it does not contain the activator poly(styrene sulfonate). The electrospray deposition technique solves the restacking problem and facilitates the infilling of the gel electrolyte by forming a highly porous open structure across the entire electrode. In the PEDOT/MXene multilayered electrode, the double-layer capacitance increased substantially because of a dramatic increase in the number of accessible sites through the MXene layer. Although applied to solid supercapacitors, these new supercapacitors outperform most aqueous electrolyte supercapacitors as well as other solid supercapacitors.