Hollow structured materials have shown great advantages for use in photoelectrochemical devices. However, their poor charge transport limits overall device performance. Here, we report a unique 3-D hollow architecture of TiO2 that greatly improves charge transport properties. We found that citric acid (CA) plays crucial roles in the formation of the 3-D hollow architecture. First, CA controls the hydrolysis rate of Ti ions and facilitates surface hydrolysis on templates during hydrothermal synthesis. Second, CA suppresses the growth of the carbon template at the initial reaction stage, resulting in the formation of comparatively small hollow fibers. More importantly, a prolonged hydrothermal reaction with CA enables a hollow sphere to grow into entangled hollow fibers via biomimetic swallowing growth. To demonstrate advantages of the 3-D hollow architecture for photoelectrochemical devices, we evaluated its photoelectrochemical performance, specifically the electrolyte diffusion and electron dynamics, by employing dye-sensitized solar cells as a model device. A systemic analysis reveals that the 3-D hollow architecture greatly improves both the electrolyte diffusion and electron transport compared to those of the nanoparticle and hollow sphere due to the elongated porous hollow morphology as well as the densely interconnected nanoparticles at the wall layer.