<p>Porous carbon micro/nanomaterials (PCMNSs) with controllable morphologies, structure, and particle size were prepared by one-step hydrothermal method using resorcinol/formaldehyde as carbon source, tetraethyl orthosilicate (TEOS) as a sacrificial hard-template precursor, double-chain cationic surfactant (didecyl dimethylammonium bromide (DDAB)) as a soft template, ethylenediamine (EDA) as both a base catalyst and a nitrogen precursor. As an organic base, EDA directly catalyzes both the polycondensation of resorcinol with formaldehyde to form phenolic resin oligomers and the hydrolysis–condensation of TEOS to generate silicate species. These organic and inorganic species co-assemble and interpenetrate at the cationic micelle interface, yielding composite nanospheres that serve as precursors for porous carbon. Notably, the controlled synthesis from individual carbon nanospheres to hemispherical bowl-like structures was achieved by using DDAB with two long hydrophobic chains and one hydrophilic head group as a soft template. The resulting electrode materials possess interconnected pore structures within the shell layers and exhibit excellent supercapacitor performance. Double-chain surfactant DDAB can form a unique bicontinuous structure between oil-in-water and water-in-oil at specific water/ethanol ratios, enabling precise morphology control from solid spheres to hollow spheres and bowl-shaped structures. Furthermore, the double hydrophobic chain architecture of DDAB provides greater structural flexibility compared with conventional single-chain surfactants, which allows for fine-tuning of pore size, pore size distribution, and particle morphology. By changing the dosage of EDA and the volume ratio of ethanol/deionized water mixed solution, carbon spheres with excellent spherical morphology (hollow spheres and bowl-shaped spheres), high specific surface area (382–396 m²·g⁻¹), large pore volume (0.37–0.40 cm³·g⁻¹), large pore size (3.65–9.08&#xa0;nm), and high doping of nitrogen elements (4.44–5.74 wt%) were successfully synthesized. The capacitance of supercapacitor assembled by carbon sphere reaches 146.5 F·g⁻¹, the energy density can reach 5.09 Wh·Kg⁻¹ at the current density of 1 A·g⁻¹, 221.22 F·g⁻¹ and 7.68 Wh·Kg⁻¹ at the current density of 0.2 A·g⁻¹, and an excellent rate capacity of 94% retention after 5000 cycles at 10 A·g⁻¹, all tested in a two-electrode system. Additionally, its equivalent series resistance is only 0.5 Ω and the time constant τ₀ is 0.31&#xa0;s, indicating facilitated ion diffusion within the porous structure and fast charge–discharge capability. The excellent electrochemical properties can be attributed to their unique carbon morphology and hierarchical pore structure, which features both a large ion-accessible specific surface area and efficient ion transport channels. The interconnected pore structure within the carbon sphere shells and the pore network between the spheres shorten the electrolyte ion transport distance, facilitating efficient energy storage. These structural features render this material highly promising for supercapacitor applications.</p> Graphical Abstract <p></p>