Pyrolysis coupled with gas chromatography and mass spectrometry (Py-GC-MS) is a useful technique for rapid characterization of the organic materials used in art. In the characterization of proteinaceous binders fragments from pyrolysis are of low intensity. Milk, casein, and glue, for example, are sometimes difficult to detect. In the work discussed in this paper pyrolysis-silylation, in the presence of hexamethyldisilazane, has been used for characterization of some proteinaceous binders with the objective of distinguishing between them in real samples. Piperazine-2,5-dione derivatives have been found to be pyrolytic markers of protein in the different binders. Silylated compounds arising from pyrolysis silylation of lipids and carbohydrates have been detected in egg and milk, respectively.