Functionalization of polyethylene (PE) with powerful biocides through a friendly and efficient procedure is necessary to obtain extended applications. A novel CO 2 -philic 2,2,6,6-tetramethyl-4-piperidinol (TMP)-based N-chloramine silicone was synthesized via Pt-catalyzed silane alcoholysis between the Si H of poly(methylhydrosiloxane) and O H of TMP and followed by chlorination of amine N H originating from TMP to N Cl. The TMP-based N-chloramine silicone was interpenetrated into PE using supercritical carbon dioxide (scCO 2 ) as working solvent. It was shown that the thickness of the TMP-based N-chloramine silicone layer on PE can be easily controlled by the interpenetration pressure, reaching a maximum value of 70 nm at 28 mp. The synthetic procedures and the interpenetration results were characterized by Fourier transform infrared, scanning electron microscopy, and X-ray photoelectron spectroscopy. In contrast with pristine PE that did not show biocidal ability, the TMP-based N-chloramine silicone modified PE imparted powerful antibacterial abilities, exerting total kills of both Staphylococcus aureus and Escherichia coli of~10 7 cfu mL −1 in 30 min. The biocidal functionality was durable toward washings, storage, and ultraviolet exposure and the recoverability of lost chlorines was good. The interpenetration in scCO 2 tactic provides an environmentally friendly and universal approach to functionalize inert substrates due to no needs of harmful solvent and chemical linkages with biocides.The mainly used biocidal compounds include N-halamines (Nchloramines and N-bromamines), 6-17 quaternary ammonia salts, 18-25 and heavy-metal ions. 26,27 N-halamines are famous and widely used biocidal groups since they are broad spectrum, rechargeable, very stable, and highly efficient. 28,29 Their antibacterial capacity originates from the positively charged halamines (+1) that function as oxidizing agents to oxidize or destruct enzymatic and/or metabolic activities of microorganisms. N-halamines are formed by halogenation of imide/amide/amine N H to N Cl or N Br. The corresponding structures are called imide/amide/amine N-halamines with a stability order of imide < amide < amine structures. 30 As an amine N-halamine precursor, 2,2,6,6-tetramethyl-4-piperidinol (TMP) is stable due to its hindered structure, 31 resistant to photodegradation due to its regular function as ultraviolet (UV) stabilizer, 32 and lack Additional Supporting Information may be found in the online version of this article.