The details of the structure of water are important for understanding its dielectric properties and vice versa, because the nuclei and electrons of water particles are, in essence, charges interacting with each other and with external fields. Although water has been studied like no other substance, its atomic-molecular dynamics (both individual and collective) are still under discussion. Bernal–Fowler 100-year-old paradigm, based on early diffraction data, requires critical analysis. In this chapter, I consider the history of the notion of “water structure,” which includes several milestones related to the appearance of particular experimental and theoretical methods. I discuss early electrical conductivity measurements, X-ray diffraction and neutron scattering techniques, pH measurements, isotopic tracer diffusion, nuclear magnetic resonance, and simulations of molecular dynamics. All these techniques and methods have significantly contributed to the development of the concept of hydrogen bonding in water and related substances. However, recent studies have shown that classic models still fail to reproduce the basic electrodynamic parameters of water and ice, and need to be improved.