This dataset contains experimental data acquired during the work developed for the Master’s dissertation “Hexagonal Boron Nitride/Graphite heterostructures studied by Low Energy Cathodoluminescence Spectroscopy”. The data include scanning tunneling microscopy (STM) and atomic force microscopy (AFM) images, as well as cathodoluminescence spectra acquired in an STM-based setup. The datasets comprise raw and processed data obtained under different experimental conditions, such as variations in temperature, bias voltage, beam current, acquisition time, and spatial position. STM and AFM images can be opened using Gwyddion. Spectral data are provided in plain text (.txt) format and can be opened and analyzed using standard data analysis software, such as Origin. The data support the figures, analyses, and discussions presented in the dissertation. Detailed acquisition parameters and data processing information are provided in the accompanying README files.