Bucharest mayor Adriean Vidreanu has promised "a traditional party that Romanians will never forget".
European Enlargement Commissioner Olli Rehn and German Foreign Minister Frank-Walter Steinmeier are among the politicians joining hands for a traditional circle dance in the city.
Romanians and Bulgarians plan all-night street parties on Sunday to see in the New Year and mark their countries' accession to the European Union on January 1.
At midnight, the Romanians will dance the 'Round Dance of Joy' made of тен steps especially conceived for this event, while famous Romanian pop bands and folk ensembles will perform on the stage.
The festivities will not end early on January 1, but they will continue, with the highlight being the central city of Sibiu, which has been named the 2007 European Cultural Capital alongside Luxembourg.
Romanian Parliament will hold its doors open during January 1-5 to all those wishing to visit it, also in a move meant to mark Romania's accession.
Besides the magnificent halls of the building - the worlds second-biggest after the Pentagon - the visitors will also see an exhibition on 'The Integration Through the Eyes of the Children' and an exhibition of Official Gazettes containing the laws adopted by Romanian Parliament in order to attain harmonization with the EU acquis.
Romania - the larger of the two - and Bulgaria will together boost the EU's population by 30 million, to 490 million, but will contribute just 1% to its total economic output.
The EU's borders will stretch from the Atlantic and Baltic in the west and north to the Black Sea in the southeast.