<p>Four-dimensional scanning transmission electron microscopy (4D-STEM) provides rich, atomic-scale insights into materials structures. However, extracting specific physical properties—such as polarization directions essential for understanding functional properties of ferroelectrics—remains a significant challenge. In this study, we systematically benchmark multiple machine learning models, namely ResNet, VGG, a custom convolutional neural network, and PCA-informed k-Nearest Neighbors, to automate the detection of polarization directions from 4D-STEM diffraction patterns in ferroelectric potassium sodium niobate. While models trained on synthetic data achieve high accuracy on idealized synthetic diffraction patterns of equivalent thickness, the domain gap between simulation and experiment remains a critical barrier to real-world deployment. In this context, a custom-made prototype representation training regime and PCA-based methods, combined with data augmentation and filtering, represent promising steps toward bridging this gap. Nevertheless, their reliability for real-world applications remains to be explored in future work. Error analysis reveals periodic missclassification patterns, indicating that not all diffraction patterns carry enough information for a successful classification. Additionally, our qualitative analysis demonstrates that irregularities in the model’s prediction patterns correlate with defects in the crystal structure, suggesting that supervised models could be used for detecting structural defects. These findings guide the development of robust, transferable machine learning tools for electron microscopy analysis.</p>