Hydrogen can be produced by photoelectrochemical (PEC) water splitting using a KOH solution as an electrolyte and TiO2 as a photoanode. In this work, we fabricated anatase TiO2 nanoring/nanotube arrays and TiO2 nanotube arrays using an anodic oxidation method, confirmed by field-emission scanning electron microscopy (FESEM) and X-ray diffractometry (XRD), and then conducted the photoelectrochemical experiments with 1 M KOH and Na2SO4 solutions. The bias voltage, small impedance, negative flat-band potential, large capacitance, and depletion layer width in the anatase TiO2–KOH system were observed, leading to the stable and large photocurrent density. To understand the effects of KOH on the interface properties of TiO2/H2O, the electric double layers of anatase TiO2(001), (100), (101)/KOH interfaces were further investigated by calculating the ion–surface interaction with molecular dynamics simulations. It is noted that the number density of potassium ions has the same trend as that of oxygen atoms due to the layering effect in liquids and the strongest ionic hydration of K+ on anatase (101) is observed by analyzing the radial distribution function and coordination number. In addition, the electrostatic characteristics along the TiO2/KOH interfaces were analyzed based on the Grahame double layer model. The potential drops in the outer Helmholtz layer of anatase (001), (100), and (101) surfaces are 1.08, 0.26, and 0.51 V, respectively. Compared with TiO2–H2O systems, the larger potential drops in the TiO2–KOH system explain the phenomenon that KOH solute contributes substantially to a chemical bias in PEC reactions. At the same time, we estimated the depletion layer widths of anatase TiO2(001), (100), and (101) surfaces as 37.48, 173.25, and 64.49 Å, respectively, which are of similar magnitude to the experimental results. Anatase TiO2(100) with the widest depletion layer is suggested in photocatalysis. These works provide a clear understanding of interfacial behavior of KOH on anatase TiO2 from a microscale, which can be used to explain the promotion effect of the KOH electrolyte and guide the design of TiO2 nanocrystals in the PEC system.