In　situ　grown　copper　(Cu)　metal　is　commonly　integrated　with　Cu2O　to　enhance　charge　separation　and　improve　photocatalytic　degradation　of　azo　dyes,　such　as　Orange　II　and　Methyl　orange　(MO).　However,　limited　solvent　diffusion　remains　a　critical　challenge　for　effective　pollutant　removal.　Inspired　by　the　dandelion　structure,　this　work　synthesizes　a　Cu/Cu2O　composite　with　an　interconnected　nanotube　structure　and　hollow　nanosphere,　facilitating　solvent　transport　and　increasing　active　surface　area.　The　optimized　Cu/Cu2O-S3　catalyst　achieves　93　%　photodegradation　efficiency　of　Orange　II　and　maintains　98　%　stability　over　five　cycles　at　a　concentration　of　100　mgL-1,　significantly　outperforming　MO.　While　previous　studies　have　attributed　this　performance　to　the　dihedral　angle　and　planarity　of　Orange　II,　the　role　of　photogenerated　electron　transport　at　the　catalyst-dye　interface　is　largely　overlooked.　Here,　this　work　reveals　that　electron　transfer　from　the　3d　orbitals　of　Cu　transfer　to　the　2p　energy　levels　of　N,　C,　O　atoms,　enhancing　carrier　mobility　and　binding　interactions.　Moreover,　the　extra　alpha-OH　group　in　Orange　II　promotes　uniform　electronic　distribution　and　planar　pi-bond　formation,　further　improving　photocatalytic　performance.　These　insights　provide　a　deeper　understanding　of　photocatalytic　mechanisms　and　offer　valuable　strategies　for　designing　more　efficient　catalysts.