Voting stations opened at 6:00 am local time under blue skies in the capital Caracas and at thousands of polling centers across the country, in a ballot widely seen as a referendum on President Nicolas Maduro's economic leadership.
Some 19.5 million people are eligible to elect lawmakers to the National Assembly, the single-chamber congress controlled for the past 16 years by late president Hugo Chavez and his successor Maduro.
Surveys by Venezuelan pollsters Datanalisis and Venebarometro have indicated a broad opposition coalition, the Democratic Unity Roundtable, is likely to win a majority of the vote.
Or it could lead to damaging political deadlock, analysts say.
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With the country suffering from soaring inflation and shortages of basic goods, the opposition is vying to force a change of course by the anti-US president.
Analysts and some political leaders have warned the vote could spark violence with a repeat of last year's anti-government protests that left 43 people dead.
It was unclear exactly how votes might translate into seats under the system of electoral constituencies, which is considered to favor the government side.