One of the major open challenges in ab initio simulations of the electrochemical interface is the determination of electrochemical barriers under a constant driving force. Existing methods to do so include extrapolation techniques based on fully explicit treatments of the electrolyte, as well as implicit solvent models which allow for a continuous variation in electrolyte charge. Emerging hybrid continuum models have the potential to revolutionize the field, since they account for the electrolyte with little computational cost while retaining some explicit electrolyte, representing a “best of both worlds” method. In this work, we present a unified approach to determine reaction energetics from fully explicit, implicit, and hybrid treatments of the electrolyte based on a new multicapacitor model of the electrochemical interface. A given electrode potential can be achieved by a variety of interfacial structures; a crucial insight from this work is that the effective surface charge gives a good proxy of the local potential, the true driving force of electrochemical processes. In contrast, we show that the traditionally considered work function gives rise to multivalued functions depending on the simulation cell size. Furthermore, we show that the reaction energetics are largely insensitive to the countercharge distribution chosen in hybrid implicit/explicit models, which means that any of the myriad implicit electrolyte models can be equivalently applied. This work thus paves the way for the accurate treatment of ab initio reaction energetics of general surface electrochemical processes using both implicit and explicit electrolytes.