The American medical chemist and pharmacologist of Russian descent earned his nickname, the 'Godfather of ecstasy', after developing a way to make the drug - and testing it out on himself to check if it worked.
A Facebook post by his wife and research partner, Ann, said he died "surrounded by family and caretakers and Buddhist meditation music".
He lived out his final years at his home in Northern California.
Shulgin began his study of organic chemistry at Harvard University in his teens and, after a stint in the US Navy during World War II, returned to Berkeley to get his PhD in biochemistry at the University of California.
During conducting research, he began experimenting with psychoactive compounds. He tested out his new creations on himself, inviting small groups of friends to join him in the tasting sessions.
During the swinging '60s, he says he made and tested hundreds of concoctions.
In 1976, he came across a compound closely related to what we now call ecstasy or MDMA - the purest available form of ecstasy.
MDMA had been previously synthesised and patented in 1912 by the pharmaceutical company Merck, but was never fully explored within humans.
Once he had fine-tuned his recipe, he introduced the chemical to a psychologist named Leo Zeff, who introduced Shulgin to a lay therapist called Ann, who later became Shulgin's wife.
Zeff used small doses of the substance in his practice as an aid to talk therapy, and introduced it to hundreds of psychologists across America.
Shortly after its introduction, ecstasy broke into the mainstream, infiltrating the club culture in many US cities and then across the world.
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