Solid preceramic polyaluminasilazane was synthesized through the reaction between liquid cyclosilazane and aluminum tri-sec-butoxide at 160 degrees C. Electrospinning of polyaluminasilazane/polyethyleneoxide (1/0.0001 mass ratio) in chloroform solutions generated smooth fibers while the electrospun fibers from the chloroform/N,N-dimethylformamide solutions had submicrometer structures on the fiber surfaces. Smooth and rough SiCNO ceramic fibers were obtained by the pyrolysis of the green fibers with an 80% yield. Superhydrophobic mats of ceramic fibers were fabricated via a chemical vapor deposition of perfluorosilane onto the rough fibers. These superhydrophobic mats possess good chemical and thermal stability.