The adsorption of hydrophobically modified poly(acrylamide)-co-(acrylic acid), designated as PAM-C14-AA (x%) (x = 5, 10, 20, representing the mole percent of acrylic acid units), at an amino-functionalized silicon surface was studied. The effect of polymer charge density was determined by varying the acrylic acid content of the copolymer. Characteristics of the adsorbed layer were evaluated by atomic force microscopy, water contact angle measurements, and X-ray photoelectron spectroscopy. The results showed that the adsorption behavior of PAM-C14-AA (x%) is influenced by the balance among the electrostatic, hydrogen-bonding, and hydrophobic interactions. Adjusting the solution pH and polymer charge density significantly affects the morphology and thickness of the adsorbed film. Furthermore, it was found that the adsorbed PAM-C14-AA undergoes conformational rearrangements when the surface is wetted by selected organic solvents. The resultant morphology and wettability of the films indicated that the different affinities of the solvents for different segments of PAM-C14-AA (x%) can be considered to be the possible cause of the conformational rearrangements of adsorbed polymer.