Multifrequency measurements in atomic force microscopy (AFM) are one of the main techniques advancing this method. Detection of the AFM probe response at different frequencies enables simultaneous and independent studies of individual constituents of overall tip–sample force and, therefore, begins to empower the advanced compositional mapping and quantitative examination of local mechanical, electromagnetic, and other properties of materials. This chapter describes the practical implementation of multifrequency measurements with a commercial instrument and, particularly, their use in AFM-based electric techniques (electric force microscopy (EFM), Kelvin force microscopy (KFM), and piezoresponse force microscopy (PFM)). One of the peculiarities of the multifrequency approach is multiple choices for a particular type of measurement. This demands a thorough evaluation of different permutations for finding the most sensitive and reliable experimental procedure. In case of EFM and KFM, the evaluation of amplitude modulation and frequency modulation detection of tip–sample electrostatic force during intermittent contact imaging revealed the more precise nature and higher spatial resolution of the frequency modulation studies. This technique has been applied for EFM and KFM imaging of various samples (metals, semiconductors, and organic self-assemblies) that have heterogeneities related to variations of work functions, strength and orientation of molecular dipoles and to a presence of surface charges. The presented results demonstrate the advanced capabilities of multifrequency measurements that are improving the nanoscale characterization of electric properties of materials.