From 2003-2007, Ezekwesili was the Federal Minister of Education under the democratically-elected President of Nigeria Olusegun Obasanjo.She was also the Chairperson of the Nigeria Extractive Industries Transprency Initiative (NEITI) and led the first ever national implementation of the global standards and principles of transparency in the oil, gas and mining sector. She had previously been the Minister of Solid Minerals (Mines and Steel) during which time she led a vibrant reform program that led to Nigeria's global recognition as a credible mining investment destination. Ezekwesili started off in the Obasanjo administration as the Pioneer head of the Budget Monitoring and Price Intelligence Unit (aka Due Process Unit). It was in this position that she earned the sobriquet of "Madam Due Process" for the outsanding work she led a team of professionals to do in sanitizing public procurement or contracting at the Federal level in Nigeria. She was the architect of the Bureau for Public Procurement legislation, the NEITI legislation and the new Minerals and Mining legislation during her six and a half years stint in government.

Prior to working for the Government of Nigeria, Ezekwesiili was working with Professor Jeffrey Sachs at the Center for International Development at Harvard.

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