Li–ZrSiO4 was synthesized by the sol-gel method. Reactions were performed with different Li:Zr molar ratios: 1, 3, 5, and 6. Cell parameters changed as follows: a0 decreased and c0 increased as the Li:Zr molar ratio increased. The x-ray photoelectron spectroscopy analysis showed two kinds of oxygen atoms. The first one was attributed to ZrSiO4 oxygens. The second one was attributed to Li–O bonds. All these results were supported by a theoretical analysis. It was concluded that lithium atoms were held in interstitial positions of the ZrSiO4 structure.