By adopting Nb2O5, HNO3 and coordination agents EDTA as raw materials, pyrochlore-free 0.64Pb(Ni1/3Nb2/3)O(3-)0.36PbTiO(3)(0.64PNN-0.36PT) powders were successfully synthesized via a combustion route. Free of pyrochlore phase was realized by the chelation formation of EDTA-metal ions which isolate niobium and lead oxides and then prevent the formation of pyrochlore phases, therein generate the desired perovskite phases. Comparing the results with similar samples synthesized by the Columbite method, the new 0.64PNN-0.36PT ceramics here shown much better dielectric and ferroelectric performances: a maximum dielectric constant of 22 856 at 1 kHz and a remnant polarization of 21.6 mu C/cm(2) at 40 kV/cm.