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Mr. Macron, an advocate of battling climate change and a leader of one of the world’s biggest agricultural producers, has been hesitant about the deal. In June, before a political agreement was reached, he threatened to block the deal if Mr. Bolsonaro pulled Brazil out of the Paris climate accord, as he had threatened to do.

“We’re asking our farmers to stop using pesticides, we’re asking our companies to produce less carbon — that has a competitiveness cost,” Mr. Macron said at the time. “So we’re not going to say from one day to the next that we’ll let in goods from countries that don’t respect any of that.”

The two presidents discussed the matter later that month, at a Group of 20 meeting in Osaka, Japan.

“Given Brazil’s attitude over the past weeks, the president of the republic can only conclude that President Bolsonaro lied to him at the Osaka summit,” Mr. Macron’s office said in a statement released on Friday morning.

“Brazil’s decisions and comments over the past weeks,” it continued, “show that President Bolsonaro has decided not to respect his obligations on climate change, nor to commit on issues related to biodiversity. Under these conditions, France is opposed to the Mercosur agreement as it stands.”

To go into effect, the trade agreement must be ratified by the European Parliament, and some member nations might insist on having their national parliaments vote on it as well. Resistance was already strong enough that Mr. Macron’s opposition could be decisive.