Recently,　the　lead-free　piezoelectric　material　Bi0.5Na0.5TiO3　(BNT)　has　been　adopted　for　piezo-catalysis　and　synergistic　catalysis,　such　as　piezo-photocatalysis.　Nonetheless,　the　catalytic　effect　of　single　BNT　is　too　weak　to　degrade　multifarious　contaminants.　Here,　BNT　and　multi-walled　carbon　nanotubes　(MWCNTs)　composite　were　prepared　and　the　catalytic　performance　of　BNT　was　prominently　boosted　by　introducing　MWCNTs　as　the　electron　capturer.　Particularly,　the　degradation　rate　of　Rhodamine　B　(RhB,　a　typical　contaminant)　could　reach　90%　within　30　min,　with　a　high　rate　constant　of　0.0805　min−1.　The　specific　degradation　pathway　of　RhB　was　analyzed.　The　formation　of　oxygen　vacancies　was　confirmed　by　XPS　analysis,　and　the　vital　role　of　oxygen　vacancies　in　the　separation　of　photo-generated　carriers　was　elucidated.　Meanwhile,　the　BNT/MWCNTs　composites　manifested　stronger　transient　current　response　compared　to　single　BNT　under　the　action　of　light　irradiation　and　ultrasonic　vibration,　respectively.　According　to　impedance　analysis,　the　composites　exhibited　lower　carrier　transport　resistance.　Eventually,　the　mechanism　of　enhanced　piezo-photocatalysis　was　explained　in　detail.　This　study　provides　an　effective　route　to　break　the　shackle　of　carrier　recombination　and　speed　up　the　carrier　transport　in　piezo-photocatalytic　materials.　©　2022　Elsevier　Ltd