Officers tracked both 27-year-old Hassan Kiko and 32-year-old Angela Magdici to a building in Romano di Lombardia in the Bergamo region in northern Italy, a spokesman for Milan police said.
The pair, having orchestrated the breakout in February, had spent a couple of weeks in the small town and appeared on the point of leaving Italy for the Middle East, he said.
A manhunt was launched after the guard helped the prisoner break out of the Limmattal jail in Zurich, freeing him from a four-year sentence for rape.
The arrest comes just days after Kiko and Magdici released a video that police said offered possible clues to their whereabouts.
The couple have been detained in police custody awaiting extradition.