Pope Benedict XVI named Sambi the Apostolic Nuncio to the United States and Permanent Observer of the Holy See to the Organization of American States on 17 December 2005. He was installed in early 2006. He toured the damage left by Hurricane Katrina during the summer of 2006, shortly after his appointment. During Pope Benedict's April 2008 visit to the U.S., Sambi accompanied the Pope and hosted him at the apostolic nunciature, where the Pope held a historic private meeting with five victims of clergy sexual abuse.