A new method is proposed for the characterization of properties of piezoelectric materials using depth-sensing indentation involving both mechanical and electrical measurements. First, a rigorous general theory is presented for axisymmetric indentation of piezoelectric solids with anisotropic properties. The theoretical results facilitate the prediction of the indentation load versus the depth of penetration of indenter into the substrate, as well as some transient electrical effects for different electrical boundary conditions. Used in conjunction with instrumented indentation experiments at the nanoscopic, microscopic or macroscopic size scales, these results lead to the prediction of some of the elastic, dielectric and piezoelectric constants as well as the activation energy for depolarization. The predictions of the theory as well as the validity of the approach have been substantiated further with detailed indentation experiments on PZT-4 and barium titanate using either a conducting indenter or an insulated indenter. The theoretical predictions of the coupled electrical-mechanical indentation of piezoelectric solids have also been checked with finite element analyses. The implications of the proposed method for the design and characterization of piezoelectric materials and for quality control in commercial production are also addressed.