Single molecules of poly(vinyl amine) are analyzed in the adsorbed state by atomic force microscopy (AFM) in two different ways. First, high-resolution images of individual adsorbed polymers were recorded in monovalent electrolyte solutions. The backbone of the imaged polymers was digitized, and the directional correlation function and internal mean-square end-to-end distance were evaluated. These quantities were analyzed with the wormlike chain (WLC) model, and the persistence length was extracted. Second, individual polymer chains were picked up from the surface, and their force–extension behavior was recorded in the same electrolyte solutions. These force profiles were also interpreted in terms of the WLC model, whereby the elastic contribution was also considered. Both techniques yield the persistence length of the polymer. From imaging one obtains a persistence length of about 1.6 nm, while the force experiments yield a value around 0.51 nm. We suspect that the force experiments reflect the intrinsic part of the persistence length, while the imaging experiments yield the persistence length including the electrostatic part.