In　this　study,　a　calcination　and　boron-doping　strategy　was　developed　to　construct　a　metal　defect-rich　B@Co1-xS　catalyst　for　Fenton-like　reaction.　Density　functional　theory　(DFT)　calculation　and　mechanistic　investigation　confirmed　that　the　enhanced　Co　vacancies　could　increase　the　adsorption　of　the　terminal　oxygen　in　the　peroxymonosulfate　(PMS)　molecules　to　the　surrounding　Co　atoms,　resulting　in　the　activation　mechanism　by　highvalent　cobalt-oxygen　species　(Co(IV)=O),　boosting　the　reaction　rate　constant　by　7.14　times.　The　B@Co1-xS/　PMS　system　possessed　excellent　interference　resistance　and　renewability　for　efficient　degradation　of　a　wide　range　of　contaminants.　Moreover,　a　continuous　flow　reactor　loaded　with　B@Co1-xS　was　developed,　which　could　operate　continuously　and　stably　with　ciprofloxacin　(CIP)　removal　efficiency　above　97　%,　proving　that　the　system　was　promising　for　applications.　Taken　all　together,　this　study　delved　into　how　to　rationally　develop　cation-deficient　transition　metal　catalysts　in　Fenton-like　systems　at　the　molecular　level,　which　was　of　critical　meaning　for　wastewater　treatment.