The ratings agency said the South American nation had failed to make $200m in repayments on its foreign debt.
Venezuela’s state-run oil company PDVSA has also been declared in default by rating agencies Fitch and Moody’s.
The news came just hours after the government met investors in Caracas to try to renegotiate its debt.
Standard & Poor (S&P)’s declares a “selective default” when a country has failed to pay one or more of its financial obligations when it came due.
In the case of Venezuela, the government of President Nicolás Maduro failed to make $200m in payments on two global bond issues by 12 November, when a 30-day grace period expired.
S&P said Venezuela is also overdue on four other bond payments worth a total of $420m but that the grace period has not yet expired on those payments.
Venezuela’s total external debt, which also includes loans from countries like Russia and China, is thought to be as much as $140bn.
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