Alivizatos served as the Minister of the Interior for one month in the Third Cabinet of Costas Simitis.

[1] On 13 February 2004, in the run-up to the 7 March legislative election, he was appointed interim Minister for the Interior, Public Administration and Decentralization in the cabinet of Kostas Simitis.

Following the electoral victory of the opposition New Democracy party, he resigned along with the rest of the cabinet on 10 March.

[2] On 17 February 2015, he was nominated by The River party as a candidate for the presidency of the Republic in the Greek presidential election, 2014–15.

On 18 February, Pavlopoulos was elected as the new President of the Republic with 233 votes in favour, while 30 were for Alivizatos, and 32 MPs (from the Communists and Golden Dawn) voted "present".