Using DFT calculations, we investigate the local structure and the distortion patterns of the perovskite AgNbO3to examine the feasibility of using silver on the perovskite A‐site in lead‐free piezoelectrics. Our calculations show that in a 5‐atom AgNbO3unit cell, silver atoms can off‐center by about 0.5 Å, forming short covalent bonds similar to the short Pb&sngbnd;O bonds in Pb‐based ferrroelectrics. In the more realistic 40‐atom supercell, Ag behaves similar to Pb in PbZrO3, forming short covalent Ag&sngbnd;O bonds through a combination of large octahedral rotations and small Ag off‐center distortions. Unlike PbZrO3, AgNbO3is not antiferroelectric due to the presence of large Nb off‐center distortions. In the AgNbO3‐PbTiO3solid solution, both A‐cations off‐center significantly and display a preference for distortion away from Nb atoms and toward Ti atoms. The interplay between this preference and maximization of local dipole alignment should lead to an MPB in the AgNbO3‐PbTiO3phase diagram. © 2003 American Institute of Physics