Hallucinogenics have been used throughout history as aphrodisiacs, though a lot of people today say that the experience just gets in the way of even thinking about sex. However, psilocybin (a.k.a. Psilocybe mexicana, Stropharia cubensis, or magic mushrooms) is a tryptamine hallucinogen whose sensory stimulation apparently includes aphrodisiac properties. There’s disagreement on the subject even among experienced users, though. Some find it no help at all; others find it an amazing aid. The recommended use is to start having sex at the highest point of the effects.
Does it count as an aphrodisiac if it enhances sex rather than increases its likelihood? I don’t think it’s quite the same category, though obviously related.
Today, psilocybin is a Schedule One drug, illegal in the United States, as are most hallucinogenics.