Vassiliou was elected to the House of Representatives of Cyprus in 1996, for the Movement of United Democrats, and re-elected in 2001 until 2006. During this time she served on the European Affairs Committee and the Joint Parliamentary Committee of Cyprus and the EU She was also an Alternate Representative of the Cyprus to the European Convention which drew up the European Constitution.
Since 2002 she has been chairperson of the board of trustees of the Cyprus Oncology Centre and she has also been President of the Cyprus Federation of Business and Professional Women since 1996.
She was involved in the United Nations Association of Cyprus, being elected as President of it for four consecutive terms, participated in numerous human rights conferences. In 1991 she was elected President of the World Federation of United Nations Associations and re-elected for two terms before being made an honorary president.
Androulla Vassiliou caused an outcry regarding a rape case, when her internet tweet was perceived as victim-blaming. She was chided for victim-shaming a 24-year-old woman who had been drugged at a hotel in Thessaloniki, Greece, on New Year's Eve.[5][6][7][8] In a third tweet, Vassiliou apologised, saying she had been misunderstood.[9][10]
1 = President. 2 = Vice President. 3 = Served from 1 January 2007. 4 = Vassiliou replaced Kyprianou on 3 March 2008. 5 = Tajani replaced Frattini on 18 June 2008. 6 = Ashton replaced Mandelson on 3 October 2008. 7 = Šemeta replaced Grybauskaitė on 1 July 2009. 8 = Samecki replaced Hübner on 4 July 2009. 9 = De Gucht replaced Michel on 17 July 2009. 10 = Šefčovič replaced Figeľ on 1 October 2009.