Molecular association between biocompatible dendritic polymers, dendrigraft poly-L-lysines (DGLs), and an anionic fluorescent probe, 8-anilino-1-naphthalenesulfonate (ANS(-)), was studied at the polarized water|1,2-dichloroethane (DCE) interface. The fluorescence intensity of ANS measured in aqueous solution was enhanced by the coexistence of DGLs over a wide pH range (2 < pH < 10), where ANS and DGL exist as a monoanionic form and a polycation, respectively. The voltammetric responses indicated that the positively charged DGLs were adsorbed at the water|DCE interface, whereas ANS(-) was transferred across the interface accompanied by the adsorption process. The interfacial behavior of the DGL-ANS associates was analyzed by potential-modulated fluorescence (PMF) spectroscopy. The PMF results demonstrated that the ion association between DGLs and ANS at the water vertical bar DCE interface is strongly affected by the applied potential and the dendritic generation of DGL. By applying appropriate potentials, the ANS anion was dissociated from its ion associate with DGLs at the interface and transferred into the organic phase, whereas DGLs remained in the aqueous phase. The Gibbs free energy of ion association (Delta G(D center dot center dot center dot ANS)) was estimated for the second-fourth generation DGLs (DGL-G2-G4) and the G4 polyamidoamine (PAMAM) dendrimer as a control. The highest stability of the DGL-G4ANS associate manifested itself through Delta G(D center dot center dot center dot ANS): DGL-G4-ANS (>G4 PAMAM dendrimer-ANS) > DGL-G3-ANS > DGL-G2-ANS. The results elucidated the efficient anion-binding ability of higher generation DGLs and its potential dependence at the liquid|liquid interface.