Ceramic nanofibers with complex structures and surface functionalities are required for improved performance in diverse applications. Fiber architecture offers a built-in directionality as well as reduction of mass transport limitation and accessibility to a large functional surface. Porous or hollow fiber structures provide additional inner surface, opening opportunities for impregnation, and creation of new interfaces within the porous body. Electrospinning is an effective method to produce continuous nanofibers of practically any material. Obtaining the desired morphology in such functional fibers is the main challenge to be addressed in this presentation. Typically, electrospun nanofibers are synthesized from solutions that contain the pre-ceramic precursors, solvents and polymers. The desired ceramic phase is obtained after drying, polymer removal and precursor’s decomposition by thermal treatment. This stage involves complex transformations in shrinkage, deformation, structure, morphology and more. The presentation will focus on creation of nanofibers with diverse surface and structures from variety of materials. Material performance will be discussed in diverse cases such as catalytic and thermoelectric systems, pointing to challenges still awaiting to be resolved.