Structural complexity and variability of the chemical properties define technological applicability of coal and demand increasing accuracy and spatial resolution from the techniques used for coal characterization for development of new, clean, and efficient technologies of coal utilization. Here, we combined spatially-resolved reflectometry, fluorescence, and confocal micro-Raman spectroscopy with high-resolution scanning probe microwave imaging to achieve a nondestructive sub-100-nm spatial resolution mapping of coal structure. It was found that this approach allows for high spatial resolution identification of individual elements in coal architecture, thus potentially generating valuable input for knowledge-driven optimization and design of coal utilization processes.