She was elected in the 2019 general election, as the first female British Ghanaian MP.

She was appointed to the official opposition frontbench in 2020, becoming the new Shadow Exchequer Secretary to the Treasury.

Oppong-Asare is of Ghanaian descent and studied Politics with International Relations at the University of Kent, where she also attained a master's degree in International Law with International Relations.

She is the chair of Labour Women's Network. From 2014 to 2018, she was a Labour Party Councillor for Erith ward on Bexley Council, serving as Deputy Leader of the opposition Labour Group from 2014 to 2016.

She has also previously served as a parliamentary assistant and constituency liaison officer and has advised the shadow minister for Preventing Violence Against Women and Girls, Seema Malhotra.

She ran to be the Labour prospective parliamentary candidate in Erith and Thamesmead when the incumbent MP Teresa Pearce announced she would stand down at the next election.

On 14 January 2020, she was announced as the Parliamentary Private Secretary to the new Shadow Secretary of State for Environment, Food, and Rural Affairs, Luke Pollard.

She was honoured in April 2020 to be asked by Labour's new Shadow Chancellor, Anneliese Dodds MP, to serve as her Parliamentary Private Secretary. 

This role means that in addition to my other work in Parliament I will also be a member of Labour’s Shadow Treasury team, helping to develop our economic policies and determine our spending priorities, and holding the Government to account.

She used her role to ensure that the concerns of local people, businesses, and public services are heard at the very highest level of the Labour Party.

On October 16, 2020, Oppong-Asare was promoted to Shadow Exchequer Secretary to the Treasury, replacing Wes Streeting, who was moved to the position of Shadow Minister for Schools following resignations the previous day relating to the Covert Human Intelligence Sources (Criminal Conduct) Bill.