"Some in Big Oil peddled the big lie," Guterres told the World Economic Forum in the Swiss Alpine village of Davos, a week after a study said ExxonMobil denied the findings of its own scientists on the role of fossil fuels in climate change.
"We learned last week that certain fossil fuel producers were fully aware in the 1970s that their core product was baking our planet," Guterres said.
"Just like the tobacco industry, they rode rough-shod over their own science," Guterres said. "And like the tobacco industry, those responsible must be held to account."
In 1998, US states won a landmark settlement against tobacco companies worth $246 billion aimed at recovering the costs of treating smokers from the harmful effects of cigarettes.
The study on ExxonMobil published in the journal Science last week found that the firm's scientists had modelled and predicted global warming "with shocking accuracy", only for the company "to spend the next couple of decades denying that very climate science".
ExxonMobil is the target of a number of lawsuits in the United States.
Asked about the Science report, an ExxonMobil spokesman said last week that the issue had come up several times in recent years and in each case the company's answer was that "those who talk about how 'Exxon Knew' are wrong in their conclusions".
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