Two-dimensional graphite films (2DGF) on solids are wonderful objects, real nature-made two-dimensional crystals. Formation on active metal surface of a 2DGF with extremely high adsorption, chemical and catalytic passivity leads to a number of staggering effects. The review is devoted to 2DGF on metals and their nature, structure, modes of formation and physico chemical properties. A nature of absorption bond between 2DGF and metal substrate is discussed in details. A special attention is paid to intercalation of 2DGF — a process when foreign atoms and even molecules (fullerenes C60 molecules) spontaneously penetrate between graphite film and metal substrate. Modes of intercalation are discussed and a mechanism of it, based on thermal movements of carbon atoms of a graphite layer, proposed earlier, is used for explanation of experimental data. A new, practically important effect-superefficient diffusion of alkaline atoms into transition metal bulk, covered by 2DGF, is reported.