Porous　and　hollow　carbon　materials　have　great　superiority　and　prospects　in　electrochemical　energy　applications,　especially　for　surface　charge　storage　due　to　the　high　active　surface.　Herein,　a　general　strategy　is　developed　to　synthesize　mesoporous　hollow　carbon　spheres　(MHCS)　with　controllable　texture　and　compositions　by　the　synergistic　effect　of　dopamine　polymerization　and　metal　catalysis　(Cu,　Bi,　Zn).　Mesoporous　MHCS–Cu　and　MHCS–Bi　are　regular　spheres,　while　mesoporous　MHCS–Zn　possesses　an　inward　concave　texture,　and　simultaneously　has　a　very　high　surface　area　of　1675.5　m2　g-1　and　lower　oxygen　content　through　the　catalytic　deoxygenation　effect.　MHCS–Zn　displays　an　exceptional　sodium　storage　kinetics　and　excellent　long　cycling　life　with　171.9　mAh　g-1　after　2500　cycles　at　5　A　g-1　in　compatible　ether-based　electrolytes.　Such　electrolyte　enables　enhanced　solvated　Na+　transport　kinetics　with　appropriate　electrostatic　interactions　at　the　surface　of　carbon　anode　as　revealed　by　molecular　dynamics　simulations　and　molecular　surface　electrostatic　potential　calculations.　Such　an　anode　also　displays　basically　constant　capacity　working　at　0 °C,　and　still　delivers　140　mAh　g-1　at　3　A　g-1　under　-20 °C.　Moreover,　MHCS–Zn　anode　is　coupled　with　Na3V2(PO4)3　cathode　to　construct　a　hybrid　capacitor,　which　exhibits　a　high　energy　density　of　145 Wh　Kg-1　at　a　very　high　power　of　8009　W　kg-1.　©　2021　Wiley-VCH　GmbH