On 17 April 2001 was named to represent the Holy See in Italy and San Marino. Pope Benedict XVI appointed Archbishop Romeo to serve as the Metropolitan Archbishop of Palermo on 19 December 2006, replacing Salvatore De Giorgi, who had reached the retirement age of 75 in September 2005. In 2005 Archbishop Romeo was awarded Knight Grand Cross of the Order of Merit of the Italian Republic. Archbishop Romeo received the pallium in St. Peter's Basilica in the Vatican on 29 June 2007 from Pope Benedict along with 45 other metropolitan archbishops. Archbishop Romeo was elected president of the Sicilian Episcopal Conference on 14 February 2007.