The French pharmaceutical company is offering Genzyme shareholders $69 per share, valuing the US biotech firm at $18.5bn (£11.8bn).
Sanofi had made the same offer to Genzyme's management in July, but was eventually turned down a month ago.
Genzyme produces treatments for high cholesterol and for rare genetic diseases, among others.
"While Sanofi-Aventis' strong preference is to engage in constructive discussions with Genzyme, Genzyme's board and management team's continued refusal to do so has led Sanofi-Aventis to commence the tender offer," said the French company in a statement.
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