The LiAlxCo1-xO2(0 <= x <= 0.7) samples were synthesized by sol-gel technique using acrylic acid as chelating agent. Rietveld refinement of high-resolution X-ray diffraction data showed that like the parent material LiCoO2, all Al doped samples have layered alpha-NaFeO2, structure (space group R (3) over barm). The Al substitution was found to introduce structural distortion around the Co atoms, which is due to change in oxygen coordination around the Co atoms and is much higher compared to that of LiCoO2 system. (c) 2006 Elsevier Ltd. All rights reserved.