To adjust the morphology and crystallinity of the chemically prepared Zr-riched` lead zirconate titanate (Pb(Zr0.95Ti0.05)O3) powders, polyethylene glycol (PEG 20000) was used in aqueous solution (modified Pechini method). Thermal analysis of the as-synthesized gel showed two distinct stages, which indicates the volatilization of water and the decomposition of polymers, respectively. When the gel were calcined at 400 oC, the powders consisted mainly of perovskite PZT accompanied with small amounts of secondary phases. The higher the calcination temperature applied, the stronger the intensity of XRD, which means the crystallinity were improved. Scanning electron microscopy of as-prepared powders suggested that the powders were soft agglomerate particles when calcined at 600 to 800 oC. Compared with the normal Pechini method, PEG could help the formation of crystalline phase and soft agglomerate. When the powders compacts were sintered at 975 to 1125 oC, high pure (>99.5%) of tetragonal phase ceramics were got having relative density of 85% to 94%.