Various agents are used for local anaesthesia. The first local anaesthetic used in clinical anaesthesia was:

The first local anesthetic, cocaine, was serendipitously discovered to have anesthetic propeies in the late 19th century. Cocaine occurs in abundance in the leaves of the coca shrub (Erythroxylon coca). Cocaine was first isolated in 1860 by Albe Niemann. Ref: Catterall W.A., Mackie K. (2011). Chapter 20. Local Anesthetics. In L.L. Brunton, B.A. Chabner, B.C. Knollmann (Eds), Goodman & Gilman's The Pharmacological Basis of Therapeutics, 12e.