The present study aims to present a comprehensive characterization of the surface of ash-layered olivine bed particles from dual fluidized bed gasification. It is well known from operation experience at industrial gasification plants that the bed material is activated during operation concerning its positive influence on gasification reactions. This is due to the built up of ash layers on the bed material particles; however, the chemical mechanisms are not well understood yet. Olivine samples from long-term operation in an industrial-scale gasification plant were investigated in comparison to fresh unused olivine. Changes of the surface morphology due to Ca-enrichment showed a significant increase of their surface area. Furthermore, the Ca-enrichment on the ash layer surface was distinctively associated to CaO being present. The presence of CaO on the surface was proven by adsorption tests of carbon monoxide as model compound. The detailed characterization contributes to a deeper understanding of the surface properties of ash layers and forms the basis for further investigations into their influence on gasification reactions.