Pb(Zr, Ti)O3-Pb(Co, Nb)O3 systems were investigated by x-ray diffraction method. System contains rhombohedral, tetragonal, and pseudocubic structures at room temperature. Crystal symmetry was changed from 4-fold symmetry to 3-fold symmetry by substituting Pb(Co1/3, Nb2/3)O3 ; PCN, to Pb(Zr0.52, Ti0.48)O3 ; PZT. As the substituted PCN concentration was increased, an increase in a-axis direction and a decrease in c-axis in the perovskite structure were occurred simultaneously, so that the crystal symmetry was changed into such way. In the higher sinteringtemperatures, the unit cell distortions occurred rather in the lower substitution range of PCN. The ferroelectric properties were maximized at the region that tetragonal and rhombohedral or pseudocubic structures were coexist.