Sol-gel derived glasses have been reported to express considerably higher bioactivity than melt-derived ones. The use of the sol-gel method for the fabrication of dental ceramic bioactive glass composites has resulted in composites consisting of an amorphous glassy network into which crystals of Calcium Silicate (CS), Wollastonite (W), leucite (Lt) and Fluorapatite (FAp) are dispersed. Thus, the aim of the present study was the investigation of the bioactivity of sol-gel derived dental ceramic/bioactive glass composites, in the form of powders and in thermally treated disk shaped specimens. Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscopy (SEM) were used to characterize the reacted products. The sol-gel derived dental glass ceramic composites present high bioactivity compared to the respective melt-derived ones, which is attributed to the higher CaO content and the crystallization of bioactive W and CS crystal phases during the fabrication process. However, the powdered samples presented faster HCAp formation compared to the respective specimens, due to their higher surface energy.