Copper-rich Cu1+δCrO2 (δ = 0–0.12) ceramics with highly c-axis orientation were synthesized by solid-state reaction in the air. The effects of copper-rich on grain alignment and electrical transport properties have been systematically investigated. While δ = 0–0.10, the ceramics are in a single phase delafossite structure, and grains grow up more than 10 times along the ab-plane, which the c-axis orientation Lotgering factors F(00l) increase from 0.17 to 0.87 and the densities increase. All the ceramics exhibit thermal activation semiconducting electrical transport behavior. Their thermal activation energy decreased from 0.303 eV to 0.209 eV, and the resistivity decreased by more than 2 orders of magnitude at room temperature. The Seebeck coefficient decreased. When δ = 0.12, the impurity CuO reduces the electrical conduction and c-axis preferred orientation. X-ray diffraction (XRD) and X-ray photoelectron spectrometer (XPS) results confirm that the acceptor Cu(Cr)2+ anti-site defects are generated by the substitution of excessive Cu ion on the Cr site, which significantly increases the hole carriers concentration. Copper-rich is observed to be efficient in enhancing the c-axis preferred orientation leading to dominant electrical transport along the ab-plane and weakened defect scattering, resulting in enhanced electrical conduction in CuCrO2 ceramic.