Manganese chlorophosphate NaPO 3 -MnCl 2 glasses were prepared via two synthetic routes and their thermal and spectroscopic properties were analyzed in order to draw a comparison between the conventional method of glass preparation, i.e. melting and quenching of the precursor salts and the so-called "coacervate route" for glass preparation. In this procedure, polyphosphate coacervates of the desired glass compositions are prepared by the mixture of an aqueous solution of the salts, separation and drying of the denser separated-phase, the coacervate. The coacervates are then melted and quenched to yield glasses. Differential Scanning Calorimetry (DSC), Differential Thermal Analysis (DTA) and Raman Spectroscopy results lead to a description of the "coacervate-derived glasses" as a system in which the polyphosphate chains are longer and mostly interconnected, when compared to the traditional glasses.