A transdermal psychoactive alkaloid composition including a psychoactive alkaloid extract or synthetic psychoactive alkaloid. The alkaloids in the extract are predominantly dephosphorylated rather than phosphorylated. The transdermal psychoactive alkaloid composition also includes an alcohol carrier, a permeation enhancer, a thickener or gelling agent, and optional further excipients. A process for obtaining a transdermal psychoactive alkaloid composition includes dephosphorylating the alkaloid during extraction, purifying the extracted alkaloid, and standardizing it to a specific concentration by adding measured quantities of excipients.