Despite the tremendous experimental and theoretical studies have been devoted to this topic, a molecular-level understanding for the effect of water adsorption energy E ads on microscopic structure and Helmholtz capacitance within EDLs remains elusive, owing to its complexity and difficulty to probe with sufficient resolution. Recently, by combining the modern theory of polarization and constant electric displacement D Hamiltonian developed by Stengel, Spaldin, and Vanderbilt, the finite-field DFTMD method is becoming an attractive technique for modeling EDLs at electrified solid-liquid interfaces. With carrying the same amount but opposite types of proton charges, the two sides of the simulated oxide surface are charged at fixed chemical composition of the supercell. In the finite-field DFTMD simulations, the average Helmholtz capacitance C H is obtained based on the supercell polarization P z . Note that the ensemble averaged supercell polarization P z converges rapidly by the application of constant electric displacement simulations, which makes the computation of C H accessible within the time-scale of DFTMD. In the previous work of applying finite-field DFTMD for modeling EDLs at both rutile TiO 2 (110)/NaCl and SnO 2 (110)/NaCl 37 interfaces, it has been found that the water chemisorption is a key factor to account for the asymmetric EDLs seen at aqueous interfaces of oxide. To further quantify the relationships between E ads , molecular structure and capacitance of EDLs on metal oxides, one of the most promising n-type oxide bismuth vanadate BiVO 4 can be selected as an example of oxide electrode with weakly chemisorbed water. BiVO 4 has been applied to photoelectrochemical water splitting and garnered considerable attention, due to its low-cost, stable, nontoxic, an ideal band gap (∼2.4 eV), and high electron-hole separation efficiencies (over 70%). In the following, we first validate the DFTMD simulations of BiVO 4 (010)/NaCl electrolyte interfaces by computing the corresponding surface pK a s and comparing them to experiments and the results of TiO 2 (110) and SnO 2 (110) surfaces. It is followed by the structural and dynamical analyses of water orientation, local coordination environment and counter-ions in the protonic double layers of BiVO 4 (010). Finally, we link the degree of asymmetry in the computed Helmholtz capacitance and the adsorption energy of water, which shows a surprising positive correlation at both metal oxide and graphene-like surfaces.