A great number of different types of materials have been used in dentistry as intermediate restoratives. Among them, new resin-based bases have been released in the dental market. The present study focuses on the identification of the organic eluates released from such materials and the study of their surface microstructure in combination with their corresponding elemental composition. For this purpose, the following materials were used:ACTIVA™BioACTIVE-BASE/LINER™, Ketac™Bond Glass Ionomer, SDR™ and Vitrebond™Light Cure Glass Ionomer Liner/Base. Methanolic leachates derived from polymerized materials were analyzed by means of gas chromatography-mass spectrometry (GC-MS). Scanning electron microscopy(SEM) was used for the surface monitoring of suitably prepared specimens. The GC-MS analysis revealed the elution of twenty different substances from the three resin-based materials, while none was eluted from the glass ionomer base. The SEM analysis for Vitrebond™ presented small pits, the one for Ketac™Bond presented elongated cracks, while no voids were present for ACTIVA™BioACTIVE-BASE/LINER™ and SDR™. Moreover, the resin matrix of some dental materials may inhibit elements' accumulation on the surface layers. Particularly, the detected organic eluents may be related to potential toxic effects.