[4] On 1 August 2001, Moloi-Moropa was sworn in to an ANC seat in the National Assembly, the lower house of the South African Parliament; she filled the casual vacancy that had arisen after Jannie Momberg's resignation.
[7][8] Less than a year later, on 14 November 2008, she returned to the National Assembly to replace Alec Erwin, who was among the several senior ANC MPs who had resigned after President Thabo Mbeki was recalled from office.
In August 2009, the Central Committee agreed unanimously to appointed her as the SACP's national deputy chairperson; she deputised Gwede Mantashe and succeeded Ncumisa Kondlo, who had died the previous year.
[2][15] In December 2012, she was additionally re-elected to a second five-year term on the ANC National Executive Committee, ranked 46th of the 80 elected members.
[18] Her tenure in that position coincided with a great deal of controversy about the governance and management of the public broadcaster, the SABC, oversight of which fell under her portfolio.
[21] ANC chief whip Stone Sizani said that Moloi-Moropa had asked to be released "to focus on her enormous responsibilities as SACP Treasurer on full-time basis, as she felt her split focus on both party and parliamentary roles did neither of them justice";[20] her departure was widely presumed to be linked to her tense relationship with Minister Muthambi.