Sodium　ion　hybrid　capacitors　(SIHCs)　address　the　high　power　and　energy　requirements　in　energy　storage　devices　but　face　significant　challenges　arising　from　the　slow　kinetics　and　cycling　instability　of　the　anode　side.　Introducing　atomic　disorder　and　employing　structural　engineering　in　anode　materials　proves　to　be　effective　strategies　for　achieving　rapid　charge　storage.　Here,　it　is　demonstrated　that　N-doped　MXene　encapsulated　amorphous　vanadium　oxide　hollow　spheres　(VOx@N-MXene　HSs)　offer　multidirectional　open　pathways　and　sufficient　vacancies,　enabling　reversible　and　fast　Na+　insertion/extraction.　Machine　learning　potentials,　coupled　with　molecular　simulation　techniques,　confirm　the　presence　of　more　abundant　pores　within　the　amorphous　vanadium　oxide　(VOx)　structure.　The　simulation　of　the　charging/discharging　process　elucidates　the　authentic　reaction　path　and　structural　evolutions　of　the　VOx@N-MXene　HSs,　providing　sufficient　insight　into　the　atomic-scale　mechanisms　associated　with　these　structural　superiorities.　The　full　SIHCs　devices　demonstrate　a　high　energy　density　of　198.3　Wh　kg−1,　along　with　a　long-term　cycling　lifespan　of　8000　cycles.　This　study　offers　valuable　strategies　into　the　intricate　design　and　exploration　of　amorphous　electrodes,　contributing　to　the　advancement　of　next-generation　electrochemical　energy　devices.　©　2024　Wiley-VCH　GmbH.