Pure osmium metal does not occur in nature. Osmium has a low crustal abundance of about 0.001 part per million. Though rare, osmium is found in native alloys with other platinum metals: in siserskite (up to 80 percent), in iridosmine (q.v.), in aurosmiridium (25 percent), and in slight amounts in native platinum. Processes for isolating it are an integral part of the metallurgical art that applies to all platinum metals.

The English chemist Smithson Tennant discovered the element together with iridium in the residues of platinum ores not soluble in aqua regia. He announced its isolation (1804) and named it for the unpleasant odour of some of its compounds (Greek osme, odour).

Of the platinum metals, osmium is the most rapidly attacked by air. The powdered metal, even at room temperature, exudes the characteristic odour of the poisonous, volatile tetroxide, OsO₄. Because solutions of OsO₄ are reduced to the black dioxide, OsO₂, by some biological materials, it is sometimes used to stain tissues for microscopic examinations.

Osmium is, with ruthenium, the most noble of the platinum metals, and cold and hot acids are without effect on them. It can be dissolved by fused alkalies, especially if an oxidizing agent such as sodium chlorate is present. Osmium will react at 200° C with air or oxygen to form OsO₄.

Osmium exhibits oxidation states from 0 to +8 in its compounds, with the exception of +1; well-characterized and stable compounds contain the element in +2, +3, +4, +6, and +8 states. There are also carbonyl and organometallic compounds in the low oxidation states −2, 0, and +1. Ruthenium is the only other element known to have an oxidation state of 8. (The chemistries of ruthenium and osmium are generally similar.) All compounds of osmium are easily reduced or decomposed by heating to form the free element as a powder or sponge. There is an extensive chemistry of the tetroxides, oxohalides, and oxo anions. There is little, if any, evidence that simple aquo ions exist, and virtually all their aqueous solutions, whatever the anions present, may be considered to contain complexes.

Natural osmium consists of a mixture of seven stable isotopes: osmium-184 (0.02 percent), osmium-186 (1.58 percent), osmium-187 (1.6 percent), osmium-188 (13.3 percent), osmium-189 (16.1 percent), osmium-190 (26.4 percent), osmium-192 (41.0 percent).