An experimental approach is presented that allows the measurement of interactions of single macromolecules at the electrolyte/single-crystal interfaces under the continuous variation of electrolyte composition. Single polyelectrolyte desorption experiments with poly(acrylic acid) were performed on atomically defined single-crystal ZnO(0001)-Zn surfaces in aqueous electrolytes of varying pH and constant ionic strength. The corresponding characterized single-crystalline surface structures were proven to be stable in the pH range of 4-11, enabling the analysis of desorption forces on both surface terraces and step edges as a function of pH. Thereby, contributions of electrostatic and van der Waals forces as well as contributions of coordinative interfacial bonds could be distinguished. The results showed that carboxylic acid functionalities adsorb weakly to hydroxide-stabilized polar ZnO(0001)-Zn surfaces with forces in the range of 60-80 pN, whereas they strongly bind to the separating step-edges between the polar terraces, most probably via coordinative bonds exhibiting forces of up to 700 pN. Thus, by means of single-molecule desorption spectroscopy individual binding sites could be readily identified by distinct features in the force-distance profiles. Moreover, the measurement of desorption forces on the large atomically flat terraces at varying pH proved that a maximum molecular desorption force occurs at pH 7 as a result of increasing repulsive interactions at pH values above the surface point of zero charge and decreasing electrostatic interactions when shifting the pH in the direction of the pK(A) of the poly(acrylic acid).