Plasma immersion ion implantation (PIII) was used to modify medical-grade PVC coated by triclosan and bronopol to enhance the antibacterial properties. The surface was first activated by O2 plasma to produce more hydrophilic groups so that triclosan and bronopol could be coated more effectively on the surface. Subsequently, an argon plasma treatment was conducted under optimal conditions to improve the antibacterial properties of the triclosan and bronopol-coated PVC samples. The modified surfaces were characterized by XPS, ATR-FTIR, SEM, and contact angle measurements. The antibacterial properties were evaluated utilizing the method of plate-counting of Staphylococcus aureus (gram positive) and Escherichia coli (gram negative). Our experimental results show that the plasma-modified PVC with bronopol exhibits good antibacterial properties while the favorable bulk properties of PVC are retained. The plasma-modified PVC with triclosan has better antibacterial performance against E. coli than bronopol. The change in the antibacterial effect on the modified PVC with time was also investigated and the antibacterial effect was observed to decrease with time.