Congress of SA Trade Unions (Cosatu) Western Cape chairman Dan Malapi said picketing had been chosen for the province because many unions were making up lost time and payment from other strikes.
Pickets would take place in Salt River, Bellville, Epping, Montague Gardens and outside the provincial legislature in Cape Town on Tuesday.
He could not estimate how many people would attend. The date for the national strike early next year was not announced.
Provincial secretary Tony Ehrenreich said KwaZulu-Natal would strike on Tuesday and Eastern Cape members would picket the same day.
On Wednesday, Mpumalanga, the Northern Cape, and Free State would take part in strikes. On Thursday, a strike was planned in Gauteng.
Malapi said the industrial action was in protest against toll roads, labour brokers, poor working conditions on farms and a lack of transformation in the provincial government, among other issues.