Piezoelectric materials based on lead zirconium titanium oxide with a composition near the morphotropic phase boundary, (Pb 0.94Sr 0.06)(Zr 0.53Ti 0.47)O 3[PSZT] have been synthesized by sol-gel method. The influence of B-site aliovalent dopant Fe 3+ on the structure, ferroelectric, dielectric, piezoelectric characteristics and microstructure have been investigated. The influence of the transition metal-oxygen vacancy defect-dipoles on the electrical characteristics have also been investigated. © 2009 Springer Science+Business Media, LLC.