Green　electrospinning　of　fully　bio-based　nanofibrous　membranes　holds　significant　promise　for　sustainable　development.　However,　the　complex　molecular　structures　and　functional　groups　inherent　in　bio-based　materials　often　lead　to　strong　intermolecular　interactions.　It　may　cause　nozzle　clogging　and　hinder　the　stretching　and　thinning　of　electrospinning　jets,　thereby　adversely　affecting　performance　optimization　and　scalable　manufacturing　of　fibers.　This　study　proposes　an　innovative　＇small-molecule　barrier＇　strategy　by　introducing　small　molecules　with　controlled　hydrogen　bonds　to　shield　strong　polymer　interactions.　It　reduced　the　jetting　resistance　of　the　microjet,　significantly　improving　the　electrospinning　efficiency　and　the　fiber　formation　quality.　Resveratrol　(RV)　and　naringin　(NRG)　were　selected　as　the　most　suitable　small　molecules,　which　increased　the　jetting　continuity　of　zein　solution　by　5.75　times　and　also　achieved　multifunctional　integration.　Furthermore,　a　sheath　gas-assisted　8-nozzle　electrospinning　device　was　used　to　significantly　increase　production　efficiency　by　11.2　times.　Most　importantly,　high-efficiency　electrospinning　of　bio-based　materials　using　water　and　ethanol　as　green　solvents　has　become　possible.　The　zein/RV/NRG　membrane　showed　better　filtration　performance　than　the　N95　mask　core　layer,　with　antibacterial　rates　against　Escherichia　coli　and　Staphylococcus　aureus　over　97　%,　and　a　ultraviolet　protection　factor　of　107.51.　This　study　advances　the　green　manufacturing　of　high-performance　multifunctional　composite　nanofibers.　©　2025　Elsevier　B.V.