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In a continuum model of the solvation of charged molecules in an aqueous solvent, the classical Poisson-Boltzmann (PB) theory is generalized to include the solute point charges and the dielectric boundary that separates the high-dielectric solvent from the low-dielectric solutes. With such a setting, we construct an effective electrostatic free-energy functional of ionic concentrations, where the solute point charges are regularized by a reaction field. We prove that such a functional admits a unique minimizer in a class of admissible ionic concentrations and that the corresponding electrostatic potential is the unique solution to the boundary-value problem of the dielectric-boundary PB equation. The negative first variation of this minimum free energy with respect to variations of the dielectric boundary defines the normal component of the dielectric boundary force. Together with the solute-solvent interfacial tension and van der Waals interaction forces, such boundary force drives an underlying charged molecular system to a stable equilibrium, as described by a variational implicit-solvent model. We develop an $L^2$-theory for the continuity and differentiability of solutions to elliptic interface problems with respect to boundary variations, and derive an explicit formula of the dielectric boundary force. With a continuum description, our result of the dielectric boundary force confirms a molecular-level prediction that the electrostatic force points from the high-dielectric and polarizable aqueous solvent to the charged molecules. Our method of analysis is general as it does not rely on any variational principles.