Polyphosphazenes (PPNs) belong to organic‐inorganic hybrid polymeric skeletal materials suitably fabricated via precipitation or condensation polymerization and self‐assembly approaches. Organic moieties with two and three −NH2 or −OH functionalities inherit subsequent ordered 2D and 3D arrangements of the atoms and molecules to attain the morphologies such as nanotubes, nano/micro‐spheres, fibers, nanosheets, and covalent organic frameworks (COFs). Auto‐doping is a strategic feature of PPN materials to originate binary‐, ternary‐, and quaternary‐doped carbon frameworks and graphitic carbon nitride (g‐C3N4) upon direct pyrolysis in an inert environment. Hollow carbon spheres provides a good range of surface areas (ca. 755–3673 m2/g) with enormous active sites and hierarchical channels for the effective flow of electrolyte ions, which make them a good choice for solid‐state batteries and supercapacitors; structural irregularities and imperfections offer surface‐adsorbed breakdown of water and open new horizons for water splitting through hydrogen evolution, oxygen evolution and oxygen reduction with the lowest half‐wave (E1/2) potential when compared to Pt/C‐ and Pt/C+RuO2‐based electrocatalysts.