The　photooxidation　of　renewable　bioderivatives　into　value-added　chemicals　is　highly　significant;　however,　it　typically　exhibits　low　selectivity　owing　to　the　challenges　in　controlling　the　oxidative　species　and　managing　the　desirable　reaction　pathways.　In　this　work,　we　used　the　Bi2O2CO3/ZnIn2S4　heterostructure,　prepared　by　a　CO2-mediated　solid-solid　phase　transition,　to　catalyze　the　photooxidation　of　bioderived　5-hydroxymethylfurfural　(HMF)　into　2,5-diformylfuran　(DFF)　with　a　high　selectivity　of　98.1%　and　a　yield　rate　of　882.6　mu　mol　g(-1)　h(-1).　The　metal　carbonate/oxide　heterointerface　enables　the　effective　transfer　of　photoactive　electrons　and　holes,　optimizes　surface　oxygen　activation,　and　facilitates　the　synergy　of　OOH　and　holes　to　selectively　convert　HMF　into　DFF.　The　findings　unravel　how　the　tailoring　and　coupling　of　the　electron-hole　pairs　and　reactive　oxygen　species　on　heterostructured　materials　can　promote　the　usage　of　renewable　feedstocks　for　sustainable　development.