This work provides a facile one-step sol-gel route to synthesize high-quality resorcinol-formaldehyde (RF) resin coated nanocomposites that can be further used to fabricate desired carbon nanostructures. Colloidal particles with different morphologies and sizes can be coated with high-quality RF resin shells by the proposed cationic surfactant assisted RF resin coating strategy. The as-synthesized RF resin coated nanocomposites are ideal candidates for selective synthesis of core-shell, hollow, and yolk-shell carbon nanostructures. Based on the carboxylic functional RF resin coating, graphitic carbon nanostructures can also be synthesized by employing the graphitization catalyst. The as-synthesized carbon nanostructures show the advantageous performances in several applications. Hollow carbon spheres are potential electrode materials for lithium-sulfur batteries. Hollow graphitic spheres are promising catalyst supports for oxygen reduction reaction. And yolk-shell structured Au@HCS nanoreactors with ultrathin shells exhibit high catalytic activity and recyclability in confined catalysis.