Polypentamethylene guanidine sulfate (PPGS), a cationic antibacterial agent with low metal corrosivity, was synthesized by replacing chloride ions in polypentamethylene guanidine hydrochloride (PPMG) with sulfate ions using anion exchange resins. The results of corrosion experiments at high temperatures and in an aqueous solution suggested that PPGS exhibited better corrosion resistance than PPMG. The synthesized PPGS exhibited lower thermal stability and degradation occurred through the removal of sulfate groups. It showed strong intrinsic antimicrobial characteristics, which could change the morphological structure and rupture cell membranes. Furthermore, the minimal inhibitory concentrations of PPGS against Escherichia coli, Staphylococcus aureus, Bacillus subtilis, and Candida albicans were approximately 8, 2, 16, and 12 ppm, respectively. Molecular simulations indicated that the positive charges accumulated on the PPGS surface can provide the driving force to attract bacteria with a negative charge on the cell membrane's phospholipid layer.