Layered transition metal oxides have a potential as catalysts for biomass conversions or as adsorbents. A better understanding of their properties is thus necessary, notably in liquid phase, where these materials have the specificity to intercalate molecules within their interlayers. To discriminate between potential catalysts or adsorbents, it is desirable to study the surface properties in the conditions of intercalation. The intercalation behaviour and acidity of four different acidic layered materials: pure tungstate phases H2W2O7, H2WO4 and mixed oxides HNbWO6 and HNbMoO6 have thus been investigated directly in liquid phase. Besides Powder X-ray diffraction, Raman spectroscopy provided valuable informations first during the preliminary protonation step and second by monitoring both the intercalation of liquid organic bases and the accessible acidity. N-alkylamines such as butylamine and octylamine were found unsuitable to discriminate the layered solids while pyridine was more selective. Pyridine did not intercalate in H2W2O7, highlighting also the lower acidity of this solid, but gave rise to new Raman features for H2WO4, HNbMoO6 and HNbWO6. Lewis and Bronsted acid sites could be discriminated from the perturbation of the inorganic layers and related to surface sites. Therefore, the characterization by Raman spectroscopy in conditions of liquid intercalation proves to efficiently evaluate layered materials. (C) 2020 Elsevier Inc. All rights reserved.