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In this short communication, we provide information on the use of the hierarchical cluster analysis of synchrotron ATR-FTIR 2D chemical imaging spectral data as a useful and powerful approach to the microspectroscopic diagnostics of molecular composition in the hybrid sound dentin/dental composite interfaces and materials, including ones developed with the use of biomimetic strategies. The described diagnostic approach can be successfully transferred to the analysis and visualisation of 2D spectral data, collected using laboratory Raman and FTIR microspectroscopy techniques.