Mr González, a retired diplomat, went from being virtually unknown to a household name after opposition leader María Corina Machado was barred from running in the election by the Maduro-controlled supreme court.
The opposition coalition, the Unitarian Democratic Platform, selected him in April as a last-minute stand-in for Ms Machado.
“A phrase that has been said to me repeatedly is ‘You are my last hope,’” Mr González said of his supporters on Thursday.
“I want to tell you that you are the hope. You have filled me with strength to face what has undoubtedly been the most unequal electoral campaign in the history of electoral processes in Venezuela.”
For over a quarter of a century, first under Hugo Chávez and now Mr Maduro, Venezuela has suffered deep and sustained economic collapse, including widespread hunger, prompting one in four citizens to flee the country.
But Ms Corina Machado, a 56-year-old industrial engineer, has given a new generation of Venezuelans hope of a brighter future as she campaigns against rampant corruption and political repression.
A tense calm blanketed Venezuela’s capital early on Monday, with businesses shuttered, bus stops empty and traffic nonexistent.
Eating breakfast on a bench next to an unopened store, 28-year-old Deyvid Cadenas, a first-time voter on Sunday, said he felt cheated.
“The majority voted for the opposition,” added Mr Cadenas. “I don’t believe yesterday’s results.”
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