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Vagner Love gave Brazil a 19th-minute lead just as the 70,000 crowd was getting impatient and the five-times world champions added four goals in a 12-minute spell late in the game.
Kaka struck twice, once with an exquisite curling shot and another with the help of a goalkeeping blunder by Daniel Viteri, and Ronaldinho and Elano also found the net.
The result was rough justice on Ecuador, who controlled the game for nearly one hour and threatened to snatch a point until Brazil's late flourish.
Brazil, the only country to have played at all 18 World Cup tournaments, have four points from their first two games in the South American group while Ecuador, attempting to qualify for their three finals in a row, have none.
"The players were very anxious and perhaps this affected their performance in the first half," Brazil coach Dunga told reporters.
Although the finale sent the crowd wild with delight, the Maracana's notoriously fickle side was also display early in the game when Brazil initially struggled to break down their rivals.
The first whistles were heard in the 16th minute but they were soon silenced by the opening goal.
Robinho sent Maicon storming down the right and he sent over a low cross which eluded Viteri and was tapped in by Vagner Love.
Brazil surprisingly failed to take control and instead handed the initiative to the visitors, who slowly came back into the game
In a tense second-half spell, Segundo Castillo was close with a 35-metre free kick and Julio Cesar had to dive desperately at the feet of Christian Benitez after Ecuador forced their way through the Brazil defence.
With an equaliser on the cards and more jeering in the crowd, the game turned dramatically Brazil's way in the 73rd minute when Kaka's low shot was diverted into the goal by Ronaldinho, wrong-footing Viteri.
Five minutes later, Kaka pounced on a loose clearance and curled in a third from nearly 30 metres.
Robinho brought the crowd to its feet by performing his trademark stepovers as he set up the fourth for Elano in the 83rd minute and Kaka completed the scoring two minutes later.
This time, his weak 25-metre shot appeared to pose no threat but slipped under Viteri and into the goal.
"I didn't see the goal because I shot very weakly and I turned my back," Kaka told Brazilian television.
