The attachment and dissociation of a proton from a water molecule and the proton transfers at solidliquid interfaces play vital roles in numerous biological, chemical processes and for the development of sustainable functional materials for energy harvesting and conversion applications. Using first-principles computational methodologies, we investigated the protonated forms of polyhedral oligomeric silsesquioxane (POSS-H+) interacting with water clusters (Wn, where n = 1-6) as a model to quantify the proton conducting and localization ability at solid-liquid interfaces. Successive addition of explicit water molecules to POSS-H+ shows that the assistance of at least three water molecules is required to dissociate the proton from POSS with the formation of an Eigen cation (H9O4+), whereas the presence of a fourth water molecule highly favors the formation of a Zundel ion (H5O2+). Reaction pathway and energy barrier analysis reveal that the formation of the Eigen cation requires significantly higher energy than the Zundel features. This confirms that the Zundel ion is destabilized and promptly converts in to Eigen ion at this interface. Moreover, we identified a Grotthuss-type mechanism for the proton transfer through a water chain close to the interface, where symmetrical and unsymmetrical arrangements of water molecules around H+ of protonated POSS-H+ are involved in the conduction of proton through water wires where successive Eigen-to-Zundel and Zundel-to-Eigen transformations are observed in quick succession.