The main focus of the study presented in this thesis is the investigation of polyelectrolytes on solid substrates with the atomic force microscope (AFM). Utilizing the AFM in both imaging and force-spectroscopy experiments, single polyelectrolyte molecules are investigated in aqueous solvents of varying ionic strength on mica. The thesis concludes with the introduction of a novel technique towards the study of polymer conformation and constitution with sub-lateral resolution called image spectroscopy (IS). IS is the successive capture and averaging of multiple image scans of features of interest and computationally uncovering sub-resolution features.