This work, by means of Raman spectroscopy, studies the vibrational modifications of a silica-based sol-gel bioactive glass (77S) in direct contact with a simple TRIS-buffered solution. The novelty of this contribution with respect to similar previous works consists in the adoption of an in situ setup, designed to avoid all kinds of external contamination. The time-dependent formation of the characteristic vibrational features of surface hydroxy-carbonate apatite (HCA) is evidenced, and followed as a function of contact time. Copyright (C) 2007 John Wiley & Sons, Ltd.