Electrospinning is a versatile process used to prepare micro- and nano-sized fibers from various polymer solution. Here, we dealt with the variation in the morphology of nylon 6 electrospun nanofibers and their polymorphism depending on the type and physical state of the collectors. SEM study showed that the fiber diameter was increased from 80 to 103 mn while it was collected in water bath. Similarly the fiber diameter and bonding was increased 103 to 115 nm with the temperature whereas it was linearly decreased 103 to 90 nm with the conductivity of the water bath. Spectroscopic analysis (FT-Raman, FT-IR) showed that the polymorphism of nylon 6 depended on the types of collector (aluminum sheet and water bath). Nylon 6 electrospun nanofibers display the gamma-phase while collected in aluminum sheet and a-phase while collection in water bath. The extent of transformation from gamma to alpha-phase was linearly increased with temperature and conductivity of the water bath.