The investigation of proton localization at a hydrophobic-hydrophilic interface is an important problem in chemical and materials sciences. In this study, protonated benzene (i.e., benzenium ion) and water clusters [BZH(+)W(n) (where n = 1-6)] are selected as prototype models to understand the interfacial interactions and proton transfer mechanism between a carbonaceous surface and water molecules. The excess protons can localize in the vicinity of the hydrophobic-hydrophilic interface, and these clusters are stabilized by various kinds of noncovalent interactions. Calculations are carried out using ab initio (MP2) and density functional theory B3LYP methods to shed more light on geometries, energetics, and spectral signatures of the protonated species [H+(H O-2)(n)] at the interfaces. These calculations revealed few low-lying isomers, which have not been reported earlier. Scrutiny of the results reveals that proton localization in the hydrophilic environment is more stable than the hydrophobic benzene pi-cloud. Furthermore, the occurrence of an O-H+center dot center dot center dot pi hydrogen bond significantly influences the O-H+center dot center dot center dot O interactions in the water clusters and also intensively affects the vibrational modes of the Eigen cation. Thus, the aromatic pi-clouds can stabilize the Eigen cation and at the same time, a twisted form of Eigen (one O-H+-pi -> two O-H+center dot center dot center dot pi) can enhance the proton transfer through the water chain via a Grotthuss-type mechanism. The vibrational spectra of these clusters reveal that there is a large red-shifted frequency for the O-H+center dot center dot center dot O, O-H+center dot center dot center dot pi, and O-H center dot center dot center dot pi modes of interaction. The energetic values and vibrational frequencies obtained from the B3LYP method are in close agreement with the MP2 level and experimental values, respectively.