In this study, polyimide(PI) nanofibers mats were prepared by electrospinning and three different fiber molphologies of random, uniaxial, and biaxial orientation were prepared by controlling the speed of drum-shaped collector and other parameters. The SEM studies reveal that the aforesaid molpholgies were obtained on the nano-fibrous mats prerared.The ionic conductivity was measured using an in-plane type conductivity tester for the PI mats soaked in the mixture of 1M lithium trifluoro-methane-sulfonate and tetra-ethylene glycol dimethyl ether. The ionic conductivity was surprisingly higher for the biaxial PI mats. For the uniaxially-oriented mats, the ionic conductivity was found to be higher in the parallel direction compared to the perpendicular direction of the fiber orientation. A curious cyclic fluctuation was found in the ionic conductivity with time. The observed behavior was explained by considering the distance between fibers and transport speed of ions used in this study.