Novel composite materials PEn (n = 1−9) have been prepared by an easily up-scalable embedding procedure of three different families of Ag(I) acylpyrazolonato complexes in polyethylene (PE) matrix. In details, PE1−PE3 composites contain polynuclear [Ag(QR)]n complexes, PE4−PE6 contain mononuclear [Ag(QR)(L)m] complexes and PE7−PE9 are loaded with mononuclear [Ag(QR) (PPh3)2] complexes, respectively (where L = 1-methylimidazole or 2-ethylimidazole, m = 1 or 2, and HQR = 1-phenyl-3- methyl-4-RC(O)-5-pyrazolone, where in detail HQfb, R = −CF2CF2CF3; HQcy, R = −cyclo-C6H11; HQbe, R = −C(H)C(CH3)2). The PEn composites, prepared by using a 1:1000 w/w silver additive/polyethylene ratio, have been characterized in bulk by IR spectroscopy and TGA analyses, which confirmed that the properties of polyethylene matrix are essentially unchanged. AFM, SEM, and EDX surface techniques show that silver additives form agglomerates with dimensions 10−100 μm on the polyethylene surface, with a slight increment of surface roughness of pristine plastic within 50 nm. However, the elastic properties of the composites are essentially the same of PE. The antibacterial activity of all composites has been tested against three bacterial strains (E. coli, P. aeruginosa and S. aureus) and results show that two classes of composites, PE1−PE3 and PE4−PE6, display high and persistent bactericidal and bacteriostatic activity, comparable to PE embedded with AgNO3. By contrast, composites PE7−PE9 exhibit a reduced antibacterial action. Contact and release tests in several conditions for specific migration of Ag+ from plastics, indicate a very limited but time persistent release of silver ions from PE1−PE6 composites, thus suggesting that they are potential antibacterial materials for future applications. Instead, PE7−PE9 almost do not release silver, only trace levels of silver ions being detected, in accordance with their reduced antibacterial action. None of the composites is toxic against higher organisms, as confirmed by D. magna test of ecotoxicity.