"Venezuela has withdrawn from the organization (and) today we will officialize our withdrawal. We have broken the historic chains of imperialism, we are an independent country, a free country and that is how it will continue to be," Rodriguez said in a TV address.
The move comes after members of the hemispheric bloc voted on Wednesday to hold another meeting of foreign affairs ministers to debate Venezuela's political and economic crises, despite the country's objections, which Venezuela said violated the bloc's own rules.
"We know that behind this gathering, this coalition of a fraction of regional governments, sights are set on the sovereignty of our country. There is an intention to intervene and instruct our country," said Rodriguez.
Relations between Venezuela and the Washington D.C.-based hemispheric bloc have been deteriorating for a while, with OAS Secretary General Luis Almagro tirelessly pursuing sanctions against the South American country for alleged democratic violations.
Almost a year ago to the day, on April 28, 2016, Almagro met with Venezuelan lawmakers from the right-wing opposition coalition, after which he announced he would invoke the OAS' Inter-American Democratic Charter against the country, which would suspend it from the bloc and pave the way for sanctions, the Venezuelan News Agency (AVN) reported on Thursday.
Shortly after, in June, Almagro organized a vote on the measure, which failed to get sufficient backing.
This year, Almagro has continued to focus his efforts on sanctioning Venezuela, as Wednesday's gathering shows, leading the South American nation to finally decided to withdraw from the hemispheric bloc.
The process of exiting the OAS will take two years, said AVN.
Meanwhile, Rodriguez said the government will continue to push for dialogue with the right-wing opposition to resolve the country's problems.
She also announced that Venezuela will take part in an emergency meeting of foreign affairs ministers from the Community of Latin American and Caribbean States (CELAC), to be held on May 2 in El Salvador.