Architectural paint analysis is an important technique for establishing the palette of historical paint colours, and reconstructing how a room or a facade might have looked at an earlier time. In its simplest form, it has often been achieved by using paint scrapes, which involves revealing a stepped sequence of layers of paint using a blade or solvents. Cross-sections are used as an alternative to, or in combination with, scrapes. Mounted cross-sections can be examined by optical microscopy. Accumulated layers of paint, wallpaper or other applied decorative finishes can be defined from their textures and colours. Knowledge of the identity of the components in paint layers can be used to reconstruct a certain paint and also to date the paint layers. It is demonstrated that micro-Raman spectroscopy combined with optical microscopy and low-vacuum scanning electron microscopy-energy-dispersive spectrometry are versatile tools for the characterization of pigments and fillers in cross-sections from architectural decorations. The paper gives an example of the examination of an interior decoration from a historical building.