Polarization dynamics in ferroelectric materials are explored via automated experiment in piezoresponse force microscopy/spectroscopy (PFM/S). A Bayesian optimization (BO) framework for imaging is developed, and its performance for a variety of acquisition and pathfinding functions is explored using previously acquired data. The optimized algorithm is then deployed on an operational scanning probe microscope (SPM) for finding areas of large electromechanical response in a thin film of PbTiO3, with results showing that, with just 20% of the area sampled, most high-response clusters were captured. This approach can allow performing more complex spectroscopies in SPM that were previously not possible due to time constraints and sample stability. Improvements to the framework to enable the incorporation of more prior information and improve efficiency further are modeled and discussed.