On 30 April 2000, Di Bello was elected mayor of Taranto with 57.5% of the votes in the ballot round. After Adriana Poli Bortone (mayor of Lecce in 1998), Rossana Di Bello is the second female mayor in Apulia, the first female mayor in the history of the city. She was reelected on 3 April 2005, obtaining 57.8% of the votes in the first round. On 18 February 2006, following the first degree sentence of one year and four months for abuse of office and false ideology in the investigation into the entrustment of the management of the city incinerator to the company Termomeccanica, she resigned from the office of mayor. She is then acquitted on appeal of all charges.