"So far we have six people dead and 22 people were rescued alive," a police spokeswoman told AFP, denying press reports of a seventh fatality.
She said another two people "are conscious under the rubble and talking with rescuers by cell phone."
Meanwhile firefighters put the number of the injured at 24, including seven in serious condition.
Television pictures showed extensive damage as rescue workers frantically sifted through rubble in search of more survivors.
A distraught woman identified by Globo television as the mother of one of the workers buried under rubble was seen imploring firefighters to locate her son.
Officials said the two-story building for the Torra Torra clothing chain store had been under construction for three months.
The cause of the accident was not yet known but an investigation is under way.
More than 20 fire department vehicles and two helicopters were on the scene.
The area was closed off to traffic to facilitate rescue work.
Such accidents involving buildings under construction or old and poorly maintained edifices occur frequently in Sao Paulo, Brazil's economic capital and most populous city.
Home to 11 million people, this sprawling metropolis is one of 12 Brazilian host cities for next year's World Cup.
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