This paper provides a brief review of current research activities that focus on the synthesis and controlled assembly of inorganic nanofibers by electrospinning, their electrical, optical and magnetic properties, as well as their applications in various areas including sensors, catalysts, batteries, filters and separators. We begin with a brief introduction to electrospinning technology and a brief method to produce ceramic nanofibers from electrospinning. We then discuss approaches to the controlled assembly and patterning of electrospun ceramic nanofibers. We continue with a highlight of some recent applications enabled by electrospun ceramic nanofibers, with a focus on the physical properties of functional ceramic nanofibers as well as their applications in energy and environmental technologies. In the end, we conclude this review with some perspectives on the future directions and implications for this new class of functional nanomaterials. It is expected that this review paper can help the readers quickly become acquainted with the basic principles and particularly the experimental procedure for preparing and assembly of 1D ceramic nanofiber and its arrays.