Photo-Fenton-like　process　of　the　Fe-based　semiconductors　depends　on　the　reversible　Fe(III)-Fe(II)　pair　strongly,　which　is　highly　sensitive　to　their　surface　structure.　Herein,　a　facile　ball-milling　method　was　developed　to　obtain　a　novel　Fe-deficient　sodium　ferric　silicate　(SFS)　by　facilitating　the　breakage　of　weak　Fe-O　bonds.　The　released　Fe3+　from　lattice　was　found,　leading　to　the　formation　of　Fe-deficient　structure　at　the　surface　of　catalyst.　Furthermore,　the　Fe-deficiency　could　be　controlled　by　adjusting　the　milling　conditions.　In　comparison　with　the　pristine　SFS,　Fe-deficient　SFS　shows　improved　transfer　efficiency　of　the　photon-activated　species　and　enhanced　photo-Fenton-like　catalytic　performances.　The　introduced　surface　Fe-deficiency　not　only　traps　photogenerated　electrons,　but　also　provides　more　active　sites　in　the　photo-Fenton-like　process.　The　removal　rate　of　ciprofloxacin　and　Cr(VI)　exhibited　5.12　and　2.83　folds　superior　to　those　of　the　pristine　counterpart,　respectively.　Furthermore,　Fe-deficient　SFS　showed　an　excellent　photocatalytic　sustainability　for　ciprofloxacin　oxidation　and　Cr(VI)　reduction.　The　possible　degradation　pathways　and　the　intermediates　of　ciprofloxacin　molecules　were　also　investigated　by　liquid　chromatograph-mass　spectrometer.　The　surface　Fe-deficient　structure　was　attributed　to　facilitating　carriers　separation　and　active　species　production　efficiently　in　this　work.