The Russian, 28, tested positive for meldonium in January and has been provisionally suspended from 12 March.
Sharapova has been suspended from “any planned activities while the investigation continues,” said the United Nations Development Programme.
She has held the role since 2007 and a UNDP spokesperson added it “remains grateful for her support of our work”.
According to the UNDP website, the organisation “works in some 170 countries and territories, helping to achieve the eradication of poverty, and the reduction of inequalities and exclusion”.
The former world number one said she has been taking meldonium for health reasons for the past 10 years.
The drug was added to the World Anti-Doping Agency’s (Wada) banned list on 1 January and Sharapova provided a positive test at the Australian Open later in the month.
Sportswear company Nike, Swiss watchmaker Tag Heuer and German carmaker Porsche had already halted their relationships with Sharapova.
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