The march is expected to start at the old Putco bus depot in Pretoria's Marabastad in the morning and head onto the N1 towards Johannesburg.
Last month, Congress of SA Trade Union provincial secretary Dumisani Dakile said the action would be carried out in other provinces as well to ensure it became a "national act".
The second protest would be held on February 25 in Pretoria at the opening of the Gauteng legislature.
"People there [at the opening] were invited to wear suits and ties. We will wear t-shirts and demonstrate with the workers, we will fight for the scrapping of e-tolling," said Dakile previously.
The third protest would be held on March 7, the anniversary of Cosatu's nationwide strike last year against e-tolling and labour broking.
Dakile said the protests last year were "a taste of what is to come".
"Even if it means that there must be action every week... until government listens to us, we are prepared to do so," Dakile said.
On January 25, the North Gauteng High Court granted the Opposition to Urban Tolling Alliance (Outa) leave to take the matter to the Supreme Court of Appeal in Bloemfontein.
Outa had applied to appeal a 13 December 2012 judgment, which dismissed its bid to have the electronic tolling of Gauteng's major roads scrapped.
Dakile said Cosatu hoped renewed protests would elicit a response from government.