Polydimethylsiloxane (PDMS) has excellent physical–chemical properties and good biocompatibility. Thus, PDMS has been widely applied in biomedical applications. However, the low surface free energy and surface hydrophobicity of PDMS can easily lead to adverse symptoms, such as tissue damage and ulceration, during medical treatment. Therefore, the construction of a hydrophilic low-friction surface on the PDMS surface could be helpful for alleviating patient discomfort and would be of great significance for broadening the application of PDMS in the field of interventional medical catheters. Existing surface modification methods such as hydrogel coatings and chemical grafting suffer from several deficiencies including uncontrollable thickness, surface fragility, and low surface strength. In this study, a hydrophilic surface with ultra-low friction properties was prepared on the surface of PDMS by an ultraviolet light (UV) curing method. The monomer acrylamide (AM) was induced by a photoinitiator to form a coating on the surface of the silicone rubber by in situ polymerization. The surface roughness of the as-prepared coatings was regulated by adding different concentrations of 2-acrylamido-2-methylpropanesulfonic acid (AMPS) to the monomer solution, and the coating properties were systematically characterized. The results indicated that the roughness and thickness of the as-prepared coatings decreased with increasing AMPS concentration and the as-prepared coatings had good hydrophilicity and low-friction properties. The Coefficient of Friction (CoF) was as low as 0.0075 in the deionized water solution, which was 99.7% lower than that of the unmodified PDMS surface. Moreover, the coating with a lower surface roughness exhibited better low-friction properties. The results reported herein provide new insight into the preparation of hydrophilic, low-friction coatings on polymer surfaces.