This paper outlines techniques developed at the Conservation Analytical Laboratory, Smithsonian Institution, for the preparation of thick cross sections (50 microns and up) and microtomed cross sections (10 microns and up) of small samples from works of art. The sectioning methods discussed here enable us to maximize the information that can be retrieved from samples of paint films. One advantage of the 10-micron microtomed sections is that they are thin enough to be analyzed non-destructively using transmission Fourier transform infrared spectrometry (FTIR). These results can be used as the first material classification step in our analytical materials identification scheme. We can then proceed using destructive chemical and physical tests of thin-sections with greater confidence. The identification of the binding media and pigments from several cross sections is also described.