Electrospinning is a simple, versatile, and cost effective method for generating nanoscale fibers, wires, and tubes. Nanowires and nanotubes could be important building blocks for nanoscale electronics, optoelectronics, and sensors as they can function as miniaturized devices as well as electrical interconnects. We report on a simple method to fabricate free standing ceramic nanofiber heterostructures, which exhibit rectifying behavior of a p-n junction.