Ceramic alumina nanofibers were prepared by plasma-assisted calcination (PAC) using atmospheric pressure plasma. Electrospun polyvinyl pyrrolidone/aluminium butoxide fibers were pre-treated by plasma generated in ambient air using a special type of coplanar dielectric barrier discharge. The effect of plasma on fibers and structural, chemical and crystalline properties of obtained ceramic nanofibers were characterized using X-Ray Photoelectron Spectroscopy and Scanning Electron Microscopy, Energy-dispersive X-ray Spectroscopy and X-Ray Diffraction. Thermogravimetric and differential thermal analysis were used for the study of thermal behaviour of untreated and plasma-treated samples. The ceramic fibers prepared by PAC exhibit suitable chemical composition, higher porosity, high length of fibers and better crystalline properties with simultaneous simplifying of the sintering process. The plasma pre-treatment of fibers results in a shortening of following thermal treatment, decrease of the required temperature and excludes a slow temperature increase as prevention of fibrous structure degradation typical in preparation of ceramic fibers by polymer-template techniques.