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This chapter describes the principles, theoretical background, recent developments, and applications of a local probe-based technique for nondestructive highresolution ferroelectric domain imaging and manipulation-piezoresponse force microscopy (PFM). This technique has proven to be a powerful tool for the characterization of ferroelectric thin films, ceramics, and single crystals. Recent advances in application of PFM for studying a mechanism of polarization reversal at the nanoscale, domain dynamics, degradation effects, and size-dependent phenomena in ferroelectrics are reviewed in detail. Examples of using PFM for the characterization of various polar materials such as ferroelectric films, piezoelectric semiconductors, and ferroelectric relaxors are given.