Exit polls released after the close of voting stations by the private survey organization Apoyo gave Garcia nearly 53 per cent support compared to 47 per cent for Humala.
The winner will get a five-year term to succeed wildly unpopular President Alejandro Toledo.
Garcia is a former president whose administration was widely unpopular, while Humala is feared by Peru's middle and upper classes.
More than half of Peru's 27 million people live in poverty.
Polls before the election indicated that the race was 57-year-old Garcia's to lose, though Humala, 43, was the top vote-getter in the first round of elections in April.
Despite a disastrous term in office from 1985-90, observers expected Garcia to win a solid majority.
While Humala has support among the lower class, his campaign is eyed with suspicion among the upper and middle classes.
Humala, who has never held elected office, has sought to stir up the anger of poor Peruvians against the upper class. Observers say Humala was hurt by an endorsement from Venezuela's leftwing nationalist President Hugo Chavez.
leaves Garcia, who presided over a shrinking economy and runaway inflation during his own administration, could be on the verge of a second chance. The Social Democratic candidate has likely benefited more from supporters of conservative candidate Lourdes Flores, who was edged out by Garcia for second place in April's first-round vote.
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