Angelo Molinari, an experienced distiller, had the idea of producing a liqueur similar to the anise-based spirits drunk since the 1800s. He created Molinari Sambuca in 1944 and it is still produced by his children and grandchildren at their purpose built distillery.

Molinari are the only producers allowed to call their Sambuca "Extra", a term added to signify the products quality and a brand term recognised by the Italian courts.