The microstructure is a critical factor governing the functionality of ceramic materials. Meanwhile, microstructural analysis of electron microscopy images of polycrystalline ceramics, which are geometrically complex and composed of countless crystal grains with porosity and secondary phases, has generally been performed manually by human experts. Objective pixel-based analysis (semantic segmentation) with high accuracy is a simple but critical step for quantifying microstructures. In this study, we apply neural network-based semantic segmentation to secondary electron images of polycrystalline ceramics obtained by three-dimensional (3D) imaging. The deep-learning-based models (e.g., fully convolutional network and U-Net) by employing a dataset based on a 3D scanning electron microscopy with a focused ion beam is found to be able to recognize defect structures characteristic of polycrystalline materials in some cases due to artifacts in electron microscopy imaging. Owing to the training images with improved depth accuracy, the accuracy evaluation function, intersection over union (IoU) values, reaches 94.6% for U-Net. These IoU values are among the highest for complex ceramics, where the 3D spatial distribution of phases is difficult to locate from a 2D image. Moreover, we employ the learned model to successfully reconstruct a 3D microstructure consisting of giga-scale voxel data in a few minutes. The resolution of a single voxel is 20 nm, which is higher than that obtained using a typical X-ray computed tomography. These results suggest that deep learning with datasets that learn depth information is essential in 3D microstructural quantifying polycrystalline ceramic materials. Additionally, developing improved segmentation models and datasets will pave the way for data assimilation into operando analysis and numerical simulations of in situ microstructures obtained experimentally and for application to process informatics.