Under the surveillance programme, the US swept up data from billions of telephone calls and emails that have passed through Brazil, including her own.
She also called on the General Assembly to create a framework of Internet regulation to stop the US and other nations from using it as the 'new battlefield' of espionage.
Addressing the UN General Assembly on the first day of its annual meeting, Rousseff accused the US of violating Brazil's sovereignty with what she called a 'grave violation of human rights and of civil liberties'.
According to stuff.co.nz, she has also cancelled her visit to the United States in a show of anger over the US National Security Agency programme.
Rousseff said the NSA also collected economic and strategic corporate data and messages by Brazilian diplomats, including to the United Nations, and from her own office.
She said Brazilian citizens' personal data 'was intercepted indiscriminately'.
Rousseff said she has demanded an apology from the US and assurances that the electronic snooping will stop.