This study presents the synthesis and characterization of degradable polyphosphoester (PPE) brushes as anti-biofouling coatings. The research focuses on creating biocompatible and biofouling-resistant surfaces using degradable polyphosphonate brushes synthesized via surface-initiated organocatalytic ring-opening polymerization (SI-ROP) on silicon surfaces. The study addresses the limitations of traditional non-degradable polymer coatings, such as inflammatory responses and bioaccumulation, by developing degradable materials that can resist biofouling and bacterial adhesion. The PPE brushes, made from 2-ethyl-2-oxo-1,3,2-dioxaphospholane (EtPPn) and 2-hexyl-2-oxo-1,3,2-dioxaphospholane (HexPPn), exhibit hydrophilic and hydrophobic properties, with thicknesses up to 55 nm. These brushes demonstrate enhanced resistance to protein and bacterial fouling, outperforming non-coated surfaces and polyester brushes. The PPE brushes show controlled degradation in aqueous media, with minimal thickness loss after 50 days. The anti-biofouling properties of the brushes were evaluated through protein adsorption, bacterial adhesion, and biofilm formation tests. The results indicate that the hydrophilic pEtPPn brushes significantly reduce the adsorption of albumin, fibrinogen, and diluted human serum, as well as bacterial adhesion of Escherichia coli and Staphylococcus aureus. The study highlights the potential of PPE brushes as degradable, anti-biofouling coatings for medical devices and artificial implant technologies. The synthesis method is efficient, reproducible, and allows for controlled brush thickness and hydrophilicity. The findings suggest that PPE brushes could be used as smart biosensing platforms due to their tunable properties and biocompatibility.This study presents the synthesis and characterization of degradable polyphosphoester (PPE) brushes as anti-biofouling coatings. The research focuses on creating biocompatible and biofouling-resistant surfaces using degradable polyphosphonate brushes synthesized via surface-initiated organocatalytic ring-opening polymerization (SI-ROP) on silicon surfaces. The study addresses the limitations of traditional non-degradable polymer coatings, such as inflammatory responses and bioaccumulation, by developing degradable materials that can resist biofouling and bacterial adhesion. The PPE brushes, made from 2-ethyl-2-oxo-1,3,2-dioxaphospholane (EtPPn) and 2-hexyl-2-oxo-1,3,2-dioxaphospholane (HexPPn), exhibit hydrophilic and hydrophobic properties, with thicknesses up to 55 nm. These brushes demonstrate enhanced resistance to protein and bacterial fouling, outperforming non-coated surfaces and polyester brushes. The PPE brushes show controlled degradation in aqueous media, with minimal thickness loss after 50 days. The anti-biofouling properties of the brushes were evaluated through protein adsorption, bacterial adhesion, and biofilm formation tests. The results indicate that the hydrophilic pEtPPn brushes significantly reduce the adsorption of albumin, fibrinogen, and diluted human serum, as well as bacterial adhesion of Escherichia coli and Staphylococcus aureus. The study highlights the potential of PPE brushes as degradable, anti-biofouling coatings for medical devices and artificial implant technologies. The synthesis method is efficient, reproducible, and allows for controlled brush thickness and hydrophilicity. The findings suggest that PPE brushes could be used as smart biosensing platforms due to their tunable properties and biocompatibility.