are named as electrochemical double layer capacitors (EDLCs) and pseudocapacitors. [13][14][15] EDLCs produce capacitance from the electrostatic charge which is accumulated at electrode/electrolyte interface producing the electrostatic charge separation; besides, the ordinary electrode materials are carbon materials, such as activated carbon, graphene, and carbon nanotubes (Figure 1a). [16,17] Carbon-based materials, such as activated carbon, [18][19][20] carbon nanofibers, [21,22] carbon nanotubes, [23][24][25] and graphene, [26][27][28][29][30] present high surface areas, good electronic conductivities, and chemical stabilities. The other approach is pseudocapacitor, in which faradic processes are generated due to electroactive species (Figure 1b). The active materials in the electroactive species contain hydroxides, transition metal oxides, and conducting polymers. [31][32][33][34] Specifically, conducting polymers present high specific capacitance; however, their weaknesses are of high cost and poor cycling stability roots in their low conductivity. Beyond that, pseudocapacitive transition metal oxides serve as admirable supercapacitor electrodes. [35][36][37] Nonetheless, the poor cycling life and low energy density impose restrictions on their practical applications, especially for two electrode supercapacitor thus encouraged us to design new electrode materials from these pseudocapacitive metal oxides. In the meanwhile, the comprehensiveness of transition metal oxides/hydroxides and carbon-based materials led to high quality of performance and arose significant attention. [34,38,39] For example, on account of the superior pseudocapacitive performance, RuO 2 has attracted increasing attention, although it exhibits a limitation in practical applications due to its high cost. [40,41] Due to the fact, RuO 2 ·xH 2 O/carbon nanofiber composites obtained by Pico et al. present high specific capacitance and long cycle life. [42] Typically, for high-performance SCs, hollow structures were investigated to increase their active surface areas and porosity for efficient transportation. [43][44][45] In addition, hollow micro/nanostructured materials have proven their valuable applications in energy storage system (Li-ion batteries [46][47][48][49][50] and SCs [51][52][53][54] ) resulting from their shell functionality [55] and novel interior geometry. Especially, the hollow nanostructure presents a competent link between electrode materials and the electrolyte, which also can improve the electrochemical performance. [56] The hollow structure also possesses far more cavities, which works as an ''ion reservoir'' and ample room, in favor of lattice expansion. [57,58] So far, it is common to obtain hollow structures via template-method and water/oil/water (W/O/W) Electrochemical capacitors (supercapacitors, SCs), have been deemed to be one of the most promising powerful electrochemical energy storage devices, owing to that SCs have long cycle lives, high power densities, and fast recharge capabilities. Transition metal oxid...