The surface properties of various vitreous fibers, suspected to be toxic to humans and animals, were investigated by means of paramagnetic labels covalently linked to the surface. Computer-aided analysis of the electron paramagnetic resonance (EPR) spectra provided structural and dynamic information on the label and its environment. Calorimetric measurements provided information on the hydration mechanism. The results were analyzed in terms of (a) different polarity and interaction abilities of surface regions, (b) presence of ions at the surface, (c) silica contents, (d) vicinity of the interacting sites, (e) fiber dimension and morphology of the surfaces, and (f) water hydration. The mobility of the labels decreased due to interaction of the fibers with ions or ionic and polar groups at the surface, Close interacting sites were identified on the basis of spin-spin effects and were distinguished and quantified in strongly and weakly interacting sites. The spin-labeling technique indicated decreased ability of the surface to interact with decreased silicon concentration and in the presence of contaminants at the surface. The interaction with water revealed in all cases a substantial heterogeneity in hydrophilicity of surface sites. The labels were not easily hydrated. Vitreous fibers of various compositions adsorbed much more water than crystalline or amorphous silica; water coordinated to surface cations played a major role in the overall adsorption. The surface reaction mechanisms were the same on fibers of different compositions, but the surface composition affected the extent of adsorption. Glass wool exhibited a much higher adsorption capacity than rock wool under the same experimental conditions. In conclusion, the combination of EPR and calorimetric measurements provided insight into the surface properties of silica-based fibers.