We report Na-Alginate-based hydrogels with high ionic conductivity and water content fabrication using poly (3,4-ethylene dioxythiophene) (PEDOT): poly (4-styrene sulfonic acid) (PSS) and a hydrogel matrix based on dimethyl sulfoxide (DMSO). DMSO was incorporated within the PEDOT:PSS hydrogel. A hydrogel with higher conductivity was created through the in-situ synthesis of intra-Na-Alginate, which was then improved upon by H2SO4 treatment. Field emission scanning electron microscopy (FESEM) was used to examine the surface morphology of the pure and synthetic hydrogel. Structural analysis was performed using Fourier-transform infrared spectroscopy (FTIR). Thermogravimetric analysis (TGA), which examines thermal properties, was also used. A specific capacitance of 312 F/g at 80 mV/s (energy density of 40.58 W/kg at a power density of 402.20 W/kg) at 100 DC mA/g was achieved by the symmetric Na-Alginate/PEDOT:PSS based flexible supercapacitor. The electrolyte achieved a higher ionic conductivity of 9.82 × 10−2 and 7.6 × 10−2 Scm−1 of Na-Alginate and a composite of Na-Alginate/PEDOT:PSS at 25 °C. Furthermore, the supercapacitor Na-Alginate/PEDOT:PSS//AC had excellent electrochemical stability by showing a capacity retention of 92.5% after 3000 continuous charge–discharge cycles at 10 mA current density. The Na- Alginate/PEDOT:PSS hydrogel displayed excellent flexibility and self-healing after re-contacting the two cut hydrogel samples of electrolyte for 90 min because of the dynamic cross-linking network efficiently dissipated energy. The illumination of a light-emitting diode (LED) verified the hydrogel’s capacity for self-healing.