Developing　highly　active　and　durable　air　cathode　catalysts　is　crucial　yet　challenging　for　rechargeable　zinc-air　batteries.　Herein,　a　size-adjustable,　flexible,　and　self-standing　carbon　membrane　catalyst　encapsulating　adjacent　Cu/Na　dual-atom　sites　is　prepared　using　a　solution　blow　spinning　technique　combined　with　a　pyrolysis　strategy.　The　intrinsic　activity　of　the　Cu-N4　site　is　boosted　by　the　neighboring　Na-containing　functional　group,　which　enhances　O2　adsorption　and　optimizes　the　rate-determining　step　of　O2　activation　(*O2 → *OOH)　during　the　oxygen　reduction　reaction　process.　Meanwhile,　the　Cu-N4　sites　are　encapsulated　within　carbon　nanofibers　and　anchored　by　the　carbon　matrix　to　form　a　C2-Cu-N4　configuration,　thereby　reinforcing　the　stability　of　the　Cu　centers.　Moreover,　the　introduction　of　Na-containing　functional　groups　on　the　carbon　atoms　significantly　reduces　the　positive　charge　on　their　outer　shell　C　atoms,　rendering　the　carbon　skeletons　less　susceptible　to　corrosion　by　oxygen　species　and　further　preventing　the　dissolution　of　Cu　centers.　Under　these　multi-type　regulations,　the　zinc-air　battery　with　Cu/Na-carbon　membrane　catalyst　as　the　air　cathode　demonstrates　long-term　discharge/charge　cycle　stability　of　over　5000 h.　This　considerable　stability　improvement　represents　a　critical　step　towards　developing　Cu-N4　active　sites　modified　with　the　neighboring　main-group　metal-containing　functional　groups　to　overcome　the　durability　barriers　of　zinc-air　batteries　for　future　practical　applications.