Chlordiazepoxide (Trade name: Librium) was the first benzodiazepine to be made commercially available. It was an accidental discovery made by Roche Pharmaceuticals in 1960. It is used as an anxiolytic and has a medium to long half life.

Roche later went on to develop chlordiazepoxide and came up with diazepam, better known as Valium, in 1963. The huge success of Valium made Roche the market leader in benzodiazepine products, and the company went on to develop and market the hypnotic nitrazepam (Mogadon) in 1965, flurazepam (Dalmane) and flunitrazepam (Rohypnol) in 1975. Other drug companies soon jumped on board the benzodiazepine band wagon, with Wyeth Pharmaceuticals introducing lorazepam (Ativan) and later Upjohn (now Pfizer)'s alprazolam (Xanax).

As prescriptions for benzodiazepines sky-rocketed through the late 1960s and 1970s the problems with dependency began to emerge, although over forty years since, chlordiazepoxide is still a useful treatment for patients suffering from acute anxiety. It is still produced and prescribed today, along side an array of other benzodiazepines, all of which have broadly similar properties to their earliest predecessor.