Articles and methods for the high-energy desorption/ionization of various compositions are disclosed. Methods of the invention utilize porous substrates, optionally in combination with one or more surface coatings and fillers, to provide enhanced desorption of analytes. Such enhanced desorption is particularly useful in fields of analysis such as mass spectrometry. This enhanced desorption has various utilities. For example, use of the porous substrate may allow desorption to be performed without the use of chemical matrices.