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Based on a combination of evidence, including surface rocks (especially ophiolites), 'xenoliths' which are rocks from deep down brought to the surface usually in volcanoes, meteorites which tell us what the overall composition of Earth probably is, seismic waves, and knowledge of the Earth's mass and moment of inertia to control the density of various layers. All this put together along with a hefty dose of theory gives us a fairly good idea that Earth has a solid iron-nickel inner core, a liquid iron-nickel outer core, a mantle of primarily of magnesium, silicon and oxygen, and a crust of similar composition but more silica rich. Oh, and course a partial covering of water we call the oceans, and an atmosphere of nitrogen and oxygen.