A method based on microwave-assisted enzymatic digestion and liquid chromatography–tandem mass spectrometry analysis is presented for the identification of proteins incorporated within solid matrices using protein standards bound to experimental cooking pottery as a validation model. The implementation of microwave irradiation allowed for a significant decrease in overall analysis time in addition to select enhancement of peptide recovery as determined by label-free relative quantitation. We envision that the reported methodology will provide new avenues for scientific discovery in areas such as archaeology and forensics. Results of this series of experiments are part of an ongoing project directed at developing a comprehensive methodology for extracting proteinaceous residues from archaeological pottery.