An innovative and economical electrospinning technique has been developed to produce polymeric nanofibers that possess high surface-to-volume ratio, tunable porosity, and desired functional properties. The ability to regulate the nanofibrous pattern and the deposition density of nanofibers in electrospinning is very challenging but highly desirable for many applications including tissue engineering and micro/nano-electronic devices. An innovative setup in which multiple electrodes, whose voltage potentials can be switched on or off, was used to produce electrospun poly(vinyl alcohol) (PVA) fibers. The electrical field and thus, the charge carrying fibers can be directed to different locations by controlling the activation time and sequence of switching between adjacent electrodes. The results show that this handy method is capable of producing nonwoven nanofibrous mats in which the fibers can have random orientations, uniaxial alignment, or multidirectional alignments. This study also demonstrates that a variety of functionally graded architectures with the desired alignments can be produced by employing a number of electrodes and switching them appropriately to obtain desired patterns. This advanced scheme of electrospinning can have a significant impact in a number of applications in health science and industrial sectors.