Casa Montero is a mining complex located outside Madrid (Spain), dated from the Early Neolithic (c. 5400–5000 cal bc). An area of some 4 ha has been investigated and some 4000 shafts recorded, of which 324 have been excavated. The characterization of its raw flint materials and the establishment of its diagnostic features are indispensable in the reconstruction of the distribution of the mine's products beyond the immediate site. This work reports the geological study of the mine's Miocene flint layers and their petrological characterization. Archaeological samples from the mine's shafts were classified according to macroscopic features and petrological characteristics.