The aqueous alkaline reaction using sodium hydroxide on polyester fibers is a well-known process to give a silk-like fabric. In this process, hydrolytic scission of ester linkages of polyester chains occurs on the fiber surface. The key parameters of this process are NaOH concentration, temperature, treatment time, and pressure of squeezing rollers. The main goal of this study was to examine the thermal comfort features of polyester woven fabrics treated with an aqueous solution of caustic soda. The findings of this study revealed that the treated and untreated woven fabrics differ significantly in terms of their vertical wicking height. The vertical wicking height of all treated samples is superior to that of the untreated one. NaOH concentration and treatment temperature were found to have a significant and negative impact on the thermal resistance of the treated fabrics. On other hand, machine speed and pressure have a positive effect on the treated fabrics. It was also found that NaOH concentration, treatment temperature, machine speed, and pressure have all a significant influence on the air permeability of treated fabrics