Four new alkaloids have been detected in South American coca leaf, coca paste and refined illicit cocaine. The compounds 3',4',5'-trimethoxycocaine (TMC), 3',4',5'trimethoxytropacocaine (TMT), 3',4',5'-trimethoxy-cis- cinnamoylcocaine (cTMCC) and 3',4',5'-trimethoxy-trans-cinnamoylcocaine (tTMCC) were isolated from the coca leaf matrix and other alkaloids by toluene extraction followed by trap and ion-pair column chromatography. The identity of each alkaloid was verified via comparison of its mass spectrum with a synthesized standard. All four alkaloids were quantitated in leaf, paste and refined samples at levels of less than 0.1% relative to cocaine via capillary gas chromatography-flame ionization detection (cGC-FID).