Rhenium does not occur free in nature or as a compound in any distinct mineral; instead it is widely distributed in small amounts in other minerals, usually in concentrations averaging about 0.001 parts per million. It occurs up to about 20 parts per million in molybdenite and to a lesser extent in sulfidic copper ores. The recovery of rhenium is aided by the concentration of its volatile heptoxide (Re₂O₇) in the flue dust and gases given off during the smelting of molybdenite ore or from its concentration with the platinum metals in the anode sludge during electrolytic copper refining. The black metal powder is extracted from the gases and dust by leaching or scrubbing them with water to dissolve the oxide, Re₂O₇, which in turn can be converted to ammonium perrhenate, NH₄ReO₄, and then reduced to the metal with hydrogen. The powder may be compressed and sintered into bars in hydrogen at elevated temperatures. Cold-working and annealing permit the fabrication of wire or foil.

Rhenium metal is silvery-white and extremely hard; it resists wear and corrosion very well and has one of the highest melting points of the elements. (The melting point of rhenium, 3,180° C 【5,756° F】, is exceeded only by that of tungsten and carbon.) The metal powder slowly oxidizes in air above 150° C (300° F) and rapidly at higher temperatures to form the yellow heptoxide, Re₂O₇. The metal is not soluble in hydrochloric acid and dissolves only slowly in other acids. There is evidence for the existence of rhenium in each of the oxidation states from −1 to +7; the most common states are +3, +4, +5, and especially +7. Rhenium's most characteristic and important compounds are formed in the oxidation states +4 and +7, although compounds are known in all formal oxidation states from −1 to +7. Perrhenic acid (HReO₄) and its anhydride, the heptoxide, and the perrhenates are common stable compounds in which rhenium is in the +7 state. Natural rhenium is a mixture of the stable isotope rhenium-185 (37.07 percent) and the radioactive rhenium-187 (62.93 percent, 7 × 10¹⁰-year half-life).