Multiphoton electron extraction spectroscopy (MEES) has been applied, for the first time, to printed documents. This spectroscopy provides molecular information from surfaces under ambient conditions, without any sample preparation. A variety of commercially available laser and inkjet printers, and many inks and toners were tested. MEES spectra of black and colored prints are presented. The results indicate that MEES provides unique fingerprinting of the printer and ink used for printing a document. Distinction between inkjet and laser printing is possible, as well as between various kinds of printers and inks used in the same category.