Silicone rubber (SR) was γ‐ray grafted with poly(methacrylic acid) (PMAA) to improve its ability to host antimicrobial drugs. Dependence of grafting yield on monomer concentration, pre‐irradiation dose, temperature and reaction time was evaluated. Modified SR films were characterized by means of FT‐IR, DSC, TGA, SEM, contact angle measurements, and swelling studies. SR‐g‐MAA showed pH sensitivity (critical pH ∼6) and good cytocompatibility. Soaking of SR‐g‐MAA in benzalkonium chloride and vancomycin aqueous solutions led to high loadings; up to 5.8 and 15.2 mg cm‐2, respectively. SR‐g‐MAA released 100% vancomycin after 24 h in buffer pH 7.4 at 37 °C, but only 20% benzalkonium chloride due to strong ionic interactions. Drug‐loaded SR‐g‐MAA prevented in vitro growth of Staphylococcus aureus. Overall, grafting of PMAA may improve the performance of SR for biomedical applications.