N-(2-Hydroxy)propyl-3-trimethylammonium chitosan chloride (HTCC) was synthesized by the reaction of glycidyltrimethylammonium chloride (GTMAC) and chitosan. The reaction product was a water-soluble chitosan derivative, and showed excellent antimicrobial activity. HTCC was blended with polyacrylonitrile (PAN) using an NaSCN aqueous solution as a common solvent. The blend solution was transparent and stable up to 6 months without phase separation. The PAN/HTCC blend fibers were prepared via a wet spinning and drawing process. Thermal, electrical, and mechanical properties as well as antimicrobial activity were investigated. It was found that the antistatic property and antimicrobial activity of the blend fibers could be achieved by adding only a small amount of HTCC.