The external sixteenth century wall paintings of St. Dumitru’s Church in Suceava (Romania) are suffering visually from deterioration. Fragments of these paintings spallated from the external wall have been studied by micro-Raman microscopy in order to elucidate possible causes of this process. Calcite and α-quartz are the components of the substratum indicating that the artists used the Roman fresco technique comprising a limewash putty. No organic binders have been detected in the substrate or pigment application. Amorphous carbon and goethite, α-FeOOH, have been identified in areas containing residues of grey and yellow pigments, respectively. Small amounts of gypsum have been detected in the grey areas which we attribute to special attention being given to surface preparation and pigment application in these areas. An abundance of sodium nitrate, nitratine, microcrystals have been observed on the surfaces of many fragments which suggests that a biodeterioration process originating from guano deposits could have been operating in these frescoes.