The suspect, detained near Venice, was "in charge of selecting and recruiting aspiring jihadists... who were then to be passed on to a Bosnian imam to be radicalized, enrolled in a terrorist organisation and transferred to a Middle Eastern war zone," investigators said.
Two other Macedonians were recently expelled from Italy over their alleged involvement in a jihadist recruitment drive.
The pair are among dozens of suspected Islamist radicals to have been banished from the country over the past year.
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Italy appears to have less of a problem with homegrown jihadists than the likes of France or Belgium, with only a small number of Italians estimated to have travelled to Syria to fight alongside IS or other groups.