Electrospun polymeric nanofibrous membranes find application in various fields such as biomedical, energy, defense, etc. The flexibility of the electrospinning process and various parameters like temperature, solvent volatility, and polymer nature helps to design nanofibers with desired properties. The wide range application of nanofibers is because of its large surface to volume ratio. The surface area of a nanofiber can be further increased by fabricating dimpled or porous fibers. In the present work, dimpled electrospun polyvinylidene fluoride-co-trifluoroethylene (P(VDF-TrFE)) nanofibers are prepared. The surface nanotopography of the fiber is studied using SEM and TEM analysis. The influence of rough surface on the wettability is evaluated by contact angle analysis. The result indicates that the nanofibrous membrane exhibits a very high contact angle (140°). In addition to this, mechanical property and thermal behavior of the membrane are also studied. The study reveals that the dimpled electrospun nanofibrous membrane is an excellent candidate in various applications where a large surface area is required.