Spin-coating of isolated positively charged macromolecules onto mica in the presence of octylamine was found to be a simple and general method of stretching and aligning the macromolecular chains. The contour length and molar mass for the stretched macromolecules can be directly measured by atomic force microscopy, which makes this method a very useful analytical tool. Moreover, the molecular height is increased by co-deposition with octylamine, which drastically improves the molecular resolution and allows even ultrathin polycations to be visualized. The reason for the key role of the octylamine is found in the formation of an ultrathin liquidlike alkylamine film, which reduces the surface energy of mica and weakens the interactions between the surface and the charged macromolecules.