The　aprotic　Li-O-2　batteries　with　high　theoretical　energy　density　hold　great　promise　for　long-range　electric　vehicles　and　grid　energy　storage　system.　However,　the　high　over-potential,　poor　cycling　stability　and　the　side　reactions　associated　with　the　carbon　electrocatalysts　at　the　cathode　limit　the　practical　application　of　Li-O-2　batteries.　To　address　these　challenges,　in　this　work,　oxygen　defect-ridden　molybdenum　oxide　(MoOx)　was　coated　on　the　surface　of　carbon　nanotubes　(CNTs)　(denoted　as　MoOx/CNT)　by　a　facile　solvothermal　reaction　for　the　first　time.　This　MoOx　layer　not　only　protects　the　CNTs　catalysts　from　the　side　reactions　but　also　promotes　the　reversible　formation　of　Li2O2,　resulting　in　low　overpotential　and　excellent　cycling　stability　of　MoOx/CNT　cathode.　A　charging　overpotential　of　only　about　0.52　V　and　an　enhanced　stability　of　more　than　210　cycles　are　obtained　for　the　as-prepared　MoOx-coated　CNT　cathode.　First-principles　study　by　density　functional　theory　(DFT)　reveals　that　the　stabilization　of　LiO2　intermediates　is　enabled　on　oxygen-defected　MoOx　during　discharge　process,　leading　to　the　formation　of　large　sheet-like　Li2O2　crystallites　that　are　easy　to　be　decomposed　during　charge　process.　This　makes　a　crucial　contribution　to　the　enhanced　electrochemical　performance　of　MoOx/CNT　cathode.