We designed substituted LiFePO4 materials having olivine-type structure by first-principle calculation for long-cycle life lithium-ion batteries. The newly designed material of Li (Fe1-xZrx) (P1-2x.Si2x) O4 is expected to have much lower volume change (3.2%) than LiFePO4. We synthesized (FeO.875ZrO.125)(PO.75Si0.25) O4by the sol-gel process. The volume change of synthesized (Fe0.875Zr0.125)P 0.75Si0.25) O4 shows good agreement with the calculated one. Moreover, the Li-ion battery using (Fe0.875Zr 0.125)P0.75Si0.25) O4 as the cathode shows excellent cycle performance. We experimentally found the smaller volume-change in (Fe0.875Zr0.125 )P 0.75Si0.25) O4 than one in LiFePO4 is due to the suppression of the shrinking FeO6 octahedra.