Maseko was born on the 2nd March 1958 in Alexandra Township, Johannesburg and grew up in Diepkloof, Soweto. Her political activism was sparked by the 1976 Soweto uprisings while a student at Orlando High School.

She was the Gauteng Provincial Treasurer of the ANC from 2''1 to 2'1' and a member of the National Executive Committee since 2'19.

She has been a parliamentarian since the dawn of democracy, serving four full terms in the Gauteng legislature from 1994 and a full term in the national parliament in 2'14. While at the Gauteng legislature she served as a member then chair of various portfolio committees and rose to become the Chief Whip of the ANC in 2''8 and then its first woman speaker after the 2''9 elections. She established the speaker’s forum in 2'11.

In the National Parliament, she served on and eventually chaired the Science and Technology Committee as well as various ad hoc committees. In 2'13, she was invited to offer training to Kenya’s 47 newly appointed county governors and speakers at the invitation of the State University of New York.

She has done extensive international work including with the Commonwealth Parliamentary Association.

Maseko received full diplomatic training from Holland, Belgium and Germany and obtained Certificate in International Relations and Diplomatic Practice from Clingendael Netherlands Institute of International relations in 1993 and a Certificate in working Technics of Development Diplomacy for Diplomats from Deutsche Stiftung fur Internationale Entwicklung (DSE) in Berlin, Schwerin, Hamburg, Bonn and Frankfurt in 1993.

She holds numerous certificates, as well as a Degree in Policy Development and Leadership & Governance with Wits School of Governance (2'16). She obtained an LLB Degree with the University of South Africa (UNISA) in 2'18 and was admitted as an Advocate of the High Court of South Africa in March 2'19. She is currently reading for her master’s degree with Wits on the Efficacy of Oversight.

She is a recipient of numerous accolades and in  2''6, was honoured as the First African Woman of Great Esteem (WGE) and conferred the Naana (Queen of Africa) title in recognition of her political involvement in women and gender empowerment by the Interfaith Kingdom Ministries (New York) in conjunction with the United Nations, and the Ghanaian Government and Parliament respectively.

She holds numerous community leadership positions, including councilor and chair St Hurbert’s Catholic Church Council.