The Stuttgart-based firm sold almost 2.1 million vehicles worldwide, marking growth of 11.3% compared with 2015, parent company Daimler said in a statement.
It was the first time Mercedes sold more than two million vehicles in a year, allowing it to reclaim the top spot it lost to its Munich rival in 2005.
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“Extraordinary growth, especially in China and Europe, has placed us at the top in the luxury segment,” said Daimler CEO Dieter Zetsche.
Mercedes had achieved its best year ever by sales for the sixth time in a row, he added.
China was a powerful growth market, with Mercedes boosting sales there by 26.6% over the year.
While the group also saw double-digit sales growth in Europe, adding 12.4%, US business shrank slightly by 0.8%.
Daimler also reported best-ever sales for its Smart compact car, which added 21% compared with 2015 to hit 144,500 vehicles sold worldwide.
BMW is set to release its figures for the full year 2016 later on Monday.
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But data issued in December showed that in the first 11 months of the year, the Munich-based manufacturer sold just over 1.8 million vehicles – 5.6% higher than in 2015, but well short of Mercedes' full-year total.
Meanwhile, Volkswagen's luxury brand Audi reported on Monday that it had sold 1.87 million vehicles in 2016, up 3.8% on the previous year but likely relegating it to third place.
The Ingolstadt-based firm suffered “strong headwinds from many important markets,” board member Dietmar Voggenreiter acknowledged.
Some Audi cars were among the Volkswagen vehicles affected by the 'dieselgate' scandal, which saw the auto giant admit to building devices designed to cheat regulatory emissions tests into 11 million vehicles worldwide. AFP
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