Barbital (or barbitone), sold under the brand names Veronal for the pure acid and Medinal for the sodium salt, was the first commercially available barbiturate.

Barbital, then called "Veronal", was first synthesized in 1902 by German chemists Emil Fischer and Joseph von Mering, who published their discovery in 1903.

A photoswitchable derivative of barbital based on a donor-acceptor Stenhouse adduct (DASA) has been developed for research purposes (photopharmacology).

[9] Japanese writer Ryūnosuke Akutagawa deliberately overdosed on the drug in 1927, as did Un Chien Andalou actor Pierre Batcheff in 1932, Hungarian poet Gyula Juhász in 1937, German mathematician Felix Hausdorff in 1942, Austrian writer Stefan Zweig in 1942, French Anarchist Germaine Berton in 1942,[10] and Greek musician Attik in 1944.

During the Holocaust, many Jewish residents of Berlin, Dresden, Wiesbaden, and other German cities used Veronal to commit suicide to avoid deportation to concentration camps by the Nazi[11] Regime.

[12] Alfred Kerr, a German theatre critic and essayist, suffered a stroke on a trip to Germany after WWII and decided to end his own life via an overdose of Veronal, which was procured for him by his wife.

[16] Barbital was also used as a plot device in the CBS television legal drama, Perry Mason, in the episode, The Case of the Missing Element (1963).