displacement, force, voltage, current, etc.), across regions up to tens to hundreds of microns wide, with nanometer resolution, enabling mesoscale materials characterization. [1] Voltage-modulated SPM techniques, such as piezoresponse force microscopy (PFM), electrochemical strain microscopy (ESM), and contact Kelvin Probe Microscopy (c-KPFM) have received particular attention due to their ability to offer functional as well as topographical characterization of materials at multiple length scales. Among these, PFM has become the premier technique for characterization of nanoscale electromechanical response, polarization switching, and domain dynamics for ferroelectric materials. Ferroelectrics are characterized by spontaneous polarization, switchable under sufficiently strong external electric fields. A clear understanding of the polarization switching process, including nucleation and growth of domains, spanning from nano-to micro-meter length scales, is crucial for assessing application of these materials in nanoscale devices. [2] In PFM an ac electric field is applied to the sample, through the conducting probe tip contact to the sample surface, resulting in electromechanical deformation of the material. [3] Scanning Probe Microscopy (SPM) based techniques probe material properties over microscale regions with nanoscale resolution, ultimately resulting in investigation of mesoscale functionalities. Among SPM techniques, piezoresponse force microscopy (PFM) is a highly effective tool in exploring polarization switching in ferroelectric materials. However, its signal is also sensitive to sample-dependent electrostatic and chemo-electromechanical changes. Literature reports have often concentrated on the evaluation of the Offfield piezoresponse, compared to On-field piezoresponse, based on the latter's increased sensitivity to non-ferroelectric contributions. Using machine learning approaches incorporating both Off-and On-field piezoresponse response as well as Off-field resonance frequency to maximize information, switching piezoresponse in a defect-rich Pb(Zr,Ti)O 3 thin film is investigated. As expected, one major contributor to the piezoresponse is mostly ferroelectric, coupled with electrostatic phenomena during On-field measurements. A second component is electrostatic in nature, while a third component is likely due to a superposition of multiple non-ferroelectric processes. The proposed approach will enable deeper understanding of switching phenomena in weakly ferroelectric samples and materials with large chemo-electromechanical response.The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/smtd.202100552.