This work was undertaken to guide the development of methods for preparing very thin polymer samples on an atomically flat, conducting surface so that the molecules could be examined with a scanning tunneling microscope. Polymer molecules with segments in an extended configuration were sought so that details of polymer structure such as branching, distances between branches, and other structural features of the molecules could be examined. Three different methods, (mechanical deformation, solution entrapment, and solution spreading) used for preparing the samples resulted in the “self-assembly” of the polymer molecules into a variety of structures which are described below.