Hundreds of bargain hunters flocked to Daka shops hoping to find electronic goods at much-reduced prices.
President Nicolas Maduro accused the Daka chain of charging exorbitant prices for the goods and said it would now be forced to have “fair prices”.
But the opposition blames government mismanagement of the economy for high inflation.
On a speech on Friday night, President Nicolas Maduro promised to sell off Daka’s stock of plasma televisions, washing machines and other merchandise.
“We’re doing this for the good of the nation. Leave nothing on the shelves, nothing in the warehouses!” he said.
Bargain hunters were quick to join overnight queues to buy the merchandise, some of it at a quarter of the price listed earlier in the week.
Nicolas Maduro said government inspectors had found goods that were overpriced by as much as 1,000%.
He said a small air-conditioning unit was selling for 36,000 bolivars ($5,730) at Daka, while the same unit cost 7,000 bolivars ($1,113) in state shops.
Daka’s owners have not responded to the allegations.
Goods at state shops are often very difficult to find and sell very quickly when available.
State shops buy dollars to pay for imported goods at the official rate of around 6.3 bolivars per dollar. But private importers often complain official dollars are not readily available and that they must buy dollars on the black market at rates about seven times higher.
The move against Daka comes after weeks of government warnings against pre-Christmas price rises.
President Nicolas Maduro often accuses wealthy businessmen of hoarding goods in order to push up prices.
But critics of his government say economic mismanagement, rather than unscrupulous retailers, is responsible for inflation and shortages of basic goods such as milk and toilet paper.
Correspondents say inflation, now running at 54%, has become an important issue in next month’s local elections.
Growing economic problems in the oil-producing nation have dented Nicolas Maduro’s popularity.
With municipal elections due across Venezuela on December 8, recent opinion polls have shown the president’s ratings have declined by about 10% in recent months.
Opposition leader Henrique Capriles – who was narrowly defeated by Nicolas Maduro in presidential elections last April – wants next month’s vote to become a quasi-referendum on the president.
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