Pauline Green studied for a diploma in business studies and she started her career as a secretary, before joining the Metropolitan Police. Later, Green studied for a degree from the Open University, then she obtained an MSc (Econ) in Comparative Government. She spent two years between 1982 and 1984 as a lecturer at Barnet College of Further Education, before becoming an assistant teacher at a Special Educational Unit. During this period Green was increasing active in local politics.
In 1985 she left her teaching career to become Parliamentary Advisor on European Affairs to the Co-operative Union, a position which she left in 1989 as her political career began.
Between 1989 and 1999 she was member of the European Parliament. During that period, she was member of the Socialist Group, member of the Bureau, Vice-Chair and Chair of the Group of the Party of European Socialists, member of the Committee on the Environment, Public Health and Consumer Protection, member of the Delegation for relations with Cyprus, member of the Delegation to the EC-Cyprus Joint Parliamentary Committee, member of the Committee on Legal Affairs and Citizens' Rights, member of the Committee on Economic and Monetary Affairs.