Cu-excess CuxAlO2 ceramics with delafossite phases were synthesized using sol-gel. In the composition range of 1≤x〈1. 04,there are no detectable non-delafossite phases. Weak diffraction peaks of CuO are observed when x ≥1.04. The room temperature conductivity of the CU1.04AlO2 sample is improved by nearly an order of magnitude over that of the CuAlO2 sample. The major defect mechanism responsible for the conductivity enhancement is proposed to be substitution defects of CuAl （Cu^2 ＋ ions substitute Al^3 ＋ ions）. The composition formula unit for Cu-excess Cux AlO2 may be expressed as Cu（All yCuy）O2.
