Electrochemical techniques provide alternative ways of measuring interfacial thermodynamic quantities through the relations between temperature, electrode potential, and capacitance. Mercury electrodes, in particular, allow the direct measurement of interfacial absolute entropies, surface tensions, excess free energies, and capacitances. In other cases, and solid electrodes in particular, the obtained information is indirect because only differential quantities are available. Therefore, the typical observables are changes of the surface tension or in the entropy. For instance, several studies demonstrated the change of entropy as a function of surface charge by using the temperature dependence of the surface capacitance and the potential of zero charge (PZC). Furthermore, the results of electrochemical measurements always depend on the electrolyte, and the extraction of pure metal-water thermodynamics is generally not possible without extrathermodynamic assumptions. While both explicit and implicit solvent models provide the means to study electrode-electrolyte interfaces at the atomic scale, relating the solid-liquid interface structures with their thermodynamic properties poses a serious challenge. Given that implicit solvent models are based on approximate free energy functionals they can directly provide thermodynamic quantities. In practice, however, their accuracy depends very sensitively on the used method and its parameterization. Several techniques are also available for computing the free energies of solid-liquid interface formation and surface tensions using explicit molecular dynamics (MD) simulations. The most straightforward method to compute the surface tension consists of evaluating the free energy change with respect to the interfacial area, that is, γ = (∂ F/∂ A). The surface tension can also be calculated from Young's equation after estimating the droplet contact angle from a MD simulation. Another way to compute the surface tension is to use its mechanical definition, which requires estimating the differences between the longitudinal and transversal pressures. Also various thermodynamic integration schemes and free energy perturbation methods have been developed for computing various interfacial thermodynamic quantities. Finally, the entropy can be directly computed by using the two-phase perturbation theory (2PT), which relies on separation of translational, rotational, and vibrational degrees of freedom (DoF) and calculating the en-tropy of each DoF from their density of state (DoS) function obtained from relatively short, ∼20 ps, MD trajectories.