N-isopropylacrylamide) (PNIPAM) has been used extensively for numerous biomedical applications. However, there is not enough information in the literature on the wettability and hygroscopic properties of electrospun PNIPAM fibers, relevant for water harvesting applications. This study focuses on investigating the wettability and hygroscopic properties of electrospun PNIPAM fibers at room temperature and elevated temperature. The wettability properties of electrospun PNIPAM fibers were compared to spin-coated PNIPAM thin films. The wettability properties of the electrospun fibers were enhanced by 56% compared to spin-coated films. Water contact angle (WCA) measured on electrospun fibers was determined to be 137° at elevated temperatures while WCA on spin cast PNIPAM film was determined to be 81° at elevated temperatures. Furthermore, hygroscopic properties of the electrospun PNIPAM fibers were studied using thermogravimetric analysis (TGA). The PNIPAM fibers are seen to exhibit moisture absorption capacity of about 16.6 wt. % under humid conditions.