Using　diamond　anodes　for　electrochemical　removal　of　recalcitrant　perfluorooctanoic　acid　(PFOA)　pollutants　has　become　an　important　strategy　in　recent　research.　However,　the　electrolysis　removal　efficiency　of　PFOA　is　still　plagued　by　low　electrochemical　active　surface　area　(EASA)　and　mass　transfer　limitation　of　conventional　flat-plate　diamond　anodes.　Herein,　the　periodic　porous　boron-doped　diamond　(PP-BDD)　anodes　were　successfully　prepared　by　3D　printing　combined　with　hot-filament　chemical　vapor　deposition　(HF-CVD)　technologies.　The　prepared　PP-BDD　anode　achieves　a　higher　PFOA　kinetics　(kapp　=　0.022　min−1,　the　normalized　rate　constant　is　6.6　m　s−1)　compared　with　the　conventional　2D-BDD　anode　(kapp　=　0.006　min−1,　the　normalized　rate　constant　is　1.8　m　s−1)　at　the　applied　density　of　20　mA　cm−2.　The　calculated　mass　transfer　coefficient　km　of　PFOA　towards　PP-BDD　(2.6　×　10−5　m　s−1)　is　about　6.1　times　higher　than　that　of　2D-BDD　(0.42　×　10−5　m　s−1),　and　the　electron　paramagnetic　resonance　(EPR)　measurement　verifies　that　PP-BDD　produces　more　•OH　and　SO4•−　radicals　during　the　electrolysis　process　versus　2D-BDD.　The　unique　periodic　pore　structure　enables　PP-BDD　higher　EASA　than　2D-BDD　and　increases　the　mass　transfer　efficiency.　Consequently,　the　number　of　electrolyte　and　PFOA　molecule　accessible　diamond　anode　surface　is　increased.　This　work　provides　valuable　guidance　for　the　deterministic　design　of　periodic　pore　structure-based　BDD　electrodes　for　efficient　electrochemical　oxidation　(EO)　of　refractory　pollutants.　©　2022　Elsevier　B.V.