In this article the changes on the surface of the 45S5 bioglass submitted to an enrichment with calcium ions were investigated. The method employed was the immersion of bioglass in calcium molten salt bath at 450°C. Changes in composition were probed by different techniques of chemical analysis. The use of SEM-EDS allowed estimating the thickness modified, as being about 10 μm. X-ray photoelectron spectroscopy enabled to infer over the structural changes on the surface of 45S5 bioactive glass. The entry of calcium in the vitreous network promoted the phase separation of microdomains rich in silica and phosphate on the surface of the glass. The formation of immiscibility region was attributed a depolymerization of silica network and also, to a possible migration of phosphate species from the bulk. The results of this study indicate a great change in the surface properties of this biomaterial. In addition, the method proposed in this study proved to be very promising in the possibility of designing the surface of bioactive glasses, to modulate the desired properties, keeping the bulk unchanged.