Electrospinning as a versatile method for preparation of nanofibers has been used to fabricate the polyvinylalcohol nanofibers containing equal molar of aluminum nitrate and copper acetate. After pretreated at 400 degrees C, the composite fibrous mats were annealed at 1100 degrees C in air for 5 h and then the delafossite-structured p-type CuAlO2 ceramics fibrous mats were obtained. The obtained CuAlO2 ceramics fibrous mats were characterized by scanning electrical microscope, X-ray diffraction and diffuse reflectance spectroscopy. The direct energy gap of the prepared CuAlO2 ceramics fibrous mats was measured to be about 3.38 eV. The CuAlO2 behaved like semiconductors and the thermally activated energy was about 0.25 eV. (C) 2009 Elsevier B.V. All rights reserved.