Molefe matriculated at Moroka High School in Thaba Nchu and studied law at the University of the North, where she completed a BProc in 1982 and an LLB in 1984.
[2] During this period, Molefe developed a specialty in corporate governance:[2] she served as an independent chairperson on various entities, including the tender board of Transnet Group, the appeals committee of the Private Security Industry Regulatory Authority, and a commission of inquiry into fatal accidents at Spoornet.
[5] During her nine years in Pretoria, Molefe's significant judgements included her 2019 ruling in favour of the Economic Freedom Fighters (EFF) in South African National Editors' Forum v EFF, in which the South African National Editors' Forum and five prominent journalists – Adriaan Basson of News24, Pauli van Wyk of the Daily Maverick, Ranjeni Munusamy of Tiso Blackstar, Barry Bateman of Eyewitness News, and Max du Preez of the Vrye Weekblad – attempted to interdict the EFF, its leader Julius Malema, and its supporters from harassing journalists on public and social media platforms.
[2] Presiding in the Equality Court, Molefe agreed with the EFF's counsel, Tembeka Ngcukaitobi, that journalists did not qualify for legal protections against discriminatory hate speech.
[10][11] Nonetheless, Molefe was one of five candidates whom the Judicial Service Commission recommended for appointment,[12] and she joined the Supreme Court of Appeal on 1 December 2022.