Psilocybe Mairei is primarily found in North Africa, specifically in Morocco and Algeria, during the months of October to December. It typically grows in clusters on soils rich in woody debris within forests containing a mix of pine (Pinus pinaster), fir (Abies pinsapo), and oak (Quercus ilicis and Quercus pyrenaica). The identification of some European collections as Psilocybe mairei has been questioned, with Guzmán in 1983 suggesting that these collections were more likely Psilocybe serbica or related species.

Although no scientific analyses have been published, the bluing reaction suggests that this species is likely potent. It is the only known wood-decomposing, bluing Psilocybe species reported from North Africa. Before the expansion of the Sahara Desert, North Africa had a more temperate climate and likely supported a greater diversity of mushrooms than what is known today. It raises the question of whether Psilocybe mairei could be a remnant of a species that was once more widespread. This thought brings to mind the cave art from the Tassili Plateau in Northern Algeria, which depicts a shamanic figure, resembling a bee, undergoing a mushroom-related experience. Notably, Psilocybe mairei is the only Psilocybe species currently documented in that region. Given that the Tassili Plateau once had abundant rivers and fertile alluvial plains, these would have been ideal habitats for mushrooms like Psilocybe mairei .

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