This paper describes an analytical approach to investigate the origin of oxalate films on marble. Calcium oxalate films were collected on buildings of historical importance in Lucca and Pisa (Italy) and characterised by optical microscopy (OM), scanning electron microscopy-energy dispersive X-ray spectrometry (SEM-EDX), Fourier transform infrared (FTIR) spectroscopy (equipped with diamond cell), and gas chromatography-mass spectrometry (GC-MS). The morphology of the films was investigated by optical and electronic microscopy. FTIR analyses highlighted the presence of calcium oxalate (both as whewellite and weddellite), gypsum, calcite, nitrates, silicates and apatite, while EDX maps showed the distribution of elements. Several samples showed traces of organic compounds, identified by GC-MS as paraffin wax, lipids of animal origin and egg. The correlation between organic material and oxalate contents suggests the origin of the films from degradation processes of past surface treatment.