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Niambi Sampson's work experience includes roles at various educational organizations. Niambi started their career in 1998 as a Baltimore Corps Member with Teach for America, where they taught 3rd grade. From 2000 to 2002, they worked as an Elementary Educator at Community Academy Public Charter School. Niambi then joined Building Excellent Schools as a National Recruiter from 2007 to 2008. From 2008 to 2016, they served as Vice President of Programs at Junior Achievement of Georgia. Currently, they hold the position of SVP- Teaching and Learning at 3DE Schools, starting in 2016.

Niambi Sampson completed their Master of Science degree in Education and Curriculum Instruction from McDaniel College from 1998 to 2000. Prior to that, they obtained their Bachelor's of Science degree in Newspaper Journalism from Florida Agricultural and Mechanical University from 1994 to 1998. In 2017, they obtained a certification in Data-driven Decision Making from Coursera.