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It is the first Olympiad since 1972 that no country has boycotted the Games, and several long-standing bans have been lifted.
A record 169 nations took part in the opening parade - a reflection of the extraordinary political changes the world has seen since the last Olympic Games at Seoul in 1988.
The opening ceremony began with the lighting of the Olympic Flame with a flaming arrow fired by paralympic archer Antonio Rebollo.
The spectacle included a staging of the mythical birth of Barcelona from the sea, complete with ocean battles between sea monsters and humans.
Opera stars who performed at the massive neo-classical Olympic Stadium at Montjuic included Placido Domingo and Jose Carerras.
But the crowd saved their loudest appreciation for Montserrat Caballe's performance of the anthem of this year's Games - the song "Barcelona", written by Queen singer Freddie Mercury who died from Aids in 1991.
There were plenty of new flags in the opening ceremony parade. Latvia and Estonia made their first independent appearance since 1936 after breaking free of Soviet rule, while neighbouring Lithuania fielded its first national team since 1928.
The collapse of the Soviet Union created a further 12 new countries, the former Soviet republics.
They have chosen to compete as one team, to be known as the Unified Team, although at medals ceremonies the flags of individual republics will be raised for winning athletes.
Germany is competing as one country for the first time since 1964, following the collapse of the Berlin Wall.
South Africa has also returned to the Olympics for the first time in 32 years after the end of apartheid.
ANC leader Nelson Mandela, who did much to attain South Africa's readmittance, was in Barcelona to see the first South African multiracial team parade at the opening ceremony.
Other countries back on the Olympic stage after long absences include Cuba, North Korea and Ethiopia.
The only last-minute controversy has been over Yugoslavia, the subject of United Nations sanctions.
In the end, it was decided Yugoslav athletes could compete as "independent Olympic participants".
Slovenia, Croatia and Bosnia-Herzegovina will have their own national teams.
The Barcelona Games was one of the most successful in recent years.
Britain's Linford Christie became the oldest champion of the Olympic 100m, winning gold at 32 years old.
Other triumphs included the record-breaking Vitaly Scherbo of Belarus, who became the first gymnast to win six gold medals in the same Olympiad.
One of the most moving moments of the Games was after the women's 10,000m final.
The winner was Derartu Tulu of Ethiopia, the first black African woman to earn an Olympic medal.
She waited for the second-placed Elana Meyer, a white South African, before setting off hand in hand for a victory lap symbolic of a new, multiracial South Africa.
This was also the Games when amateur status was lifted for the first time, producing the legendary American "Dream Team" of elite professional basketball players including stars such as Magic Johnson and Michael Jordan.
The team won an easy gold medal, and is still considered the best basketball team ever to have been put together.
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