Barium, which is slightly harder than lead, has a silvery white lustre when freshly cut. In nature it is always found combined with other elements. The Swedish chemist Carl Wilhelm Scheele (Scheele, Carl Wilhelm) discovered (1774) a new base (baryta, or barium oxide) as a minor constituent in pyrolusite, and from this base he prepared some crystals of barium sulfate, which he sent to Johan Gottlieb Gahn (Gahn, Johan Gottlieb), the discoverer of manganese. A month later Gahn found that the mineral barite is also composed of barium sulfate. Only after the electric battery became available could Sir Humphry Davy finally isolate (1808) the element itself by electrolysis.

Though barium minerals are dense, barium itself is comparatively light. Its cosmic abundance is estimated as 3.7 atoms (Si = 10⁶ atoms). Barium constitutes about 0.03 percent of the Earth's crust, chiefly as the minerals barite (also called barytes or heavy spar) and witherite. Commercial production of barium depends upon the electrolysis of fused barium chloride, but the most effective method is the reduction of the oxide by heating with aluminum or silicon in a high vacuum. A mixture of barium monoxide and peroxide can also be used in the reduction. Only a few tons of the metal are produced each year.

The metal is used as a getter in electron tubes to perfect the vacuum by combining with final traces of gases, as a deoxidizer in copper refining, and as a constituent in certain alloys (alloy). The alloy with nickel readily emits electrons when heated and is used for this reason in electron tubes and in spark plug electrodes. The presence of barium (atomic number 56) after uranium (atomic number 92) had been bombarded by neutrons was the clue that led to the recognition of nuclear fission (1939).

Naturally occurring barium is a mixture of seven stable isotopes: barium-138 (71.66 percent), barium-137 (11.32 percent), barium-136 (7.81 percent), barium-135 (6.59 percent), barium-134 (2.42 percent), barium-130 (0.101 percent), and barium-132 (0.097 percent). About twice this many radioactive isotopes have been prepared with mass numbers ranging from 126 to 143. In its compounds barium has an oxidation state of +2. The Ba²⁺ ion may be precipitated from solution by the addition of carbonate (CO₃^2-), sulfate (SO₄^2-), chromate (CrO₄^2-), or phosphate (PO₄^3-) anions. All soluble barium compounds are toxic.

Most barium compounds are produced from the sulfate via reduction to the sulfide. Barium sulfate (BaSO₄), a white, heavy powder that occurs in nature as the mineral barite, is one of the most insoluble salts known. It is widely used as a filler (e.g., in paper and rubber) and finds an important application as an opaque medium in the X-ray examination of the gastrointestinal tract, but it is principally used in oil-drilling mud. Lithopone, a mixture of barium sulfate and zinc sulfide, is a brilliant white pigment.

A number of uses of barium compounds depend on the ready formation of the highly insoluble sulfate. Thus, witherite, the compound barium carbonate (BaCO₃), perhaps the most important barium compound, is employed in removing sulfate from salt brines before they are fed into electrolytic cells (for the production of chlorine and alkali). The carbonate also is used to make other barium chemicals, as a flux in ceramics, and in the manufacture of optical glass, fine glassware, and ceramic permanent magnets for loudspeakers. Although barium carbonate is not soluble in water, it dissolves in the hydrochloric acid of the stomach and thus is used in rat poisons.

Another barium compound, barium chloride (BaCl₂·2H₂O), consisting of colourless crystals that are soluble in water, is utilized in heat-treating baths, in laboratories as a chemical reagent to precipitate soluble sulfates, and on a commercial scale with sodium sulfate to form a white filler and pigment (blanc fixe) for leather, rubber, cloth, and photographic paper. The oxygen compound barium peroxide (BaO₂) is used for both oxygen production and as a source of hydrogen peroxide. Volatile barium compounds impart a yellowish green colour to a flame owing to the emission of light of mostly two characteristic wavelengths. Barium nitrate, formed with the nitrogen-oxygen group NO₃^-, and chlorate, formed with the chlorine-oxygen group ClO₃^-, are used for this effect in green signal flares and fireworks.