The functionalization of polymeric matrices through graft polymerization offers multiple advantages by introducing new properties through the incorporation of functional chemical groups on the surface. These modifications can change the chemical properties of the matrix, such as hydrophilicity and chemical reactivity, and enable new chemical interactions with other molecules that the matrix alone could not achieve. This expands the applicability of the material in various fields, particularly in medicine, where these functionalized matrices can be employed as drug delivery systems. In this work, poly(N-vinylpyrrolidone) was incorporated through a graft polymerization of N-vinylpyrrolidone on silicone rubber catheters using gamma radiation to promote the polymerization reaction on the matrix. The graft degree of poly(N-vinylpyrrolidone) on the SR matrix was studied based on the absorbed dose and monomer concentration. Additionally, the new materials were characterized using TGA, wettability kinetics, ATR-FTIR, and Raman spectroscopy, as well as a drug loading evaluation.