Increasing environmental pollution and population compounded by a decrease in the availability of non-renewable resources and fossil fuels has propelled the need for sustainable alternate energy storage technologies particularly in the last two decades. An attempt to meet this crisis was carried out by a unique, microwave-assisted method which has enabled the generation of a novel Si, P co-doped carbon (SiPDC) for supercapacitor applications. The microwave-assisted method is useful in developing SiPDC at a rapid and economical fashion that does not employ any inert or reducing gases, but is high yielding. Varying proportions of precursor materials were utilized to generate four SiPDCs (SiPDC-1, SiPDC-2, SiPDC-3 and SiPDC-4) with varying contents of dopants as evidenced by X-ray photoelectron spectroscopic (XPS) results. Surface area and pore size analysis revealed that SiPDC-2 has a surface area of 641.51 m2 g−1, abundant micropores, mesopores and macropores which are critical for electrical double layer capacitance (EDLC). Of all the SiPDCs, SiPDC-2 exhibited highest capacitance of 276 F g−1 in 1 M H2SO4 and 244 F g−1 in 6 M KOH at a scan rate of 5 mV s−1. Galvanostatic charge–discharge studies performed in 6 M KOH establish the high capacitance of SiPDC-2. SiPDC-2 also exhibited excellent electrochemical stability in 1 M H2SO4 and 6 M KOH.