A statement from Cosatu, which investors fear is flexing its muscles only a week after political ally Jacob Zuma became President, said it would go to the North Gauteng High Court at 21:00 to try to block the deal, expected to be one of South Africa's largest share listings.
The move follows the Independent Communications Authority of South Africa's (Icasa) shock announcement on Friday of objections to the deal. In April, Icasa said it did not need regulatory approval.
The rand fell as much as 3% after Icasa demanded a public "consultation" on the deal.
Vodacom, which some analysts have valued at more than R70bn, said on Saturday it would fight the union attempt to get the courts to block the listing.
Few details
The listing stems from a plan by fixed-line operator Telkom to unbundle its 35% stake in Vodacom to shareholders after selling a 15% stake to joint Vodacom owner Vodafone.
Cosatu has opposed the deal on the grounds that it would threaten jobs and allow a foreign company - in this case, Britain's Vodafone - to own a major South African company.
Icasa has given few details of its plans for the public hearings, other than to say they should take place by mid-June.
Nobody from Icasa was available for comment on Saturday.
However, the Weekender newspaper published an SMS from Icasa councillor Marcia Socikwa that muddied the picture even further, and raised questions about its legal jurisdiction to interfere in matters relating to the Johannesburg Stock Exchange (JSE).
"Icasa has no jurisdiction on the JSE. Vodacom is a licensee and thus falls within our jurisdiction.
"A public process, based on consultation with all stakeholders, is best basis on which to make a decision."
Listing 'on track'
The paper said a subsequent message clarified that the listing could not proceed "until the public process and a subsequent decision".
JSE chiefs said the planned listing remained "on track" for Monday.
"The listing is on track and we're awaiting a decision or advice from Vodacom as to how they want to proceed," JSE Deputy Chief Executive Nicky Newton-King told Reuters.
Cosatu spokesperson Patrick Craven denied any link between the timing of the Icasa decision and Zuma's accession to the presidency on May 9.
"That's purely coincidental," Craven said. "The key question is 'What legal power does Icasa have?'"