[1] In 1976, it began to appear mixed with heroin, as an additive, and the mixture was sometimes also called "China White".

Schedule I list in September 1981, only two years after its appearance on the street, but already other fentanyl analogs were being developed.

Following the appearance of α-methylfentanyl on the market, dozens of new fentanyl analogs have been reported, starting with para-fluorofentanyl, followed by α-methylacetylfentanyl, then by the highly potent 3-methylfentanyl, and subsequently by many others such as β-hydroxyfentanyl, ohmefentanyl, β-hydroxythiofentanyl and β-hydroxy-4-methylfentanyl.

In 1991, a group of Russian chemistry students discovered a simplified synthesis route which used phosgene instead of phenethylamine.

Fentanyl analogs such as α-methylfentanyl and 3-methylfentanyl are often used as the "cut" in small amounts in normal heroin stamps and bags, making them more potent and profitable than when sold as heroin alone due to the advantage of raising the retail price and potency per unit sold.