Leonardo - who was named a United Nations Messenger of Peace last week - wrote: "This seems like the perfect setting to join Instagram and share this view from the UN General Assembly. What a great honor this is. #Climate2014 (sic)"
The 39-year-old star also posted a picture of himself looking dapper in a suit alongside UN Secretary-General Ban Ki-moon, who appointed him UN Messenger of Peace last week.
In a caption attached to the image, he wrote: "Today, I have the privilege to speak at the United Nations #Climate2014 Summit where world leaders are expected to announce the bold steps they will take to tackle climate change. Thank you Secretary-General Ban Ki-moon. (sic)"
Just two hours after posting his first Instagram picture Leonardo had already amassed more than 12,000 followers, but he was following just four people in return.
The star described himself as an actor and environmentalist in his bio on the social networking site.
Leonardo has amassed 11.1 million Twitter followers since joining the social network in April 2010.
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Leonardo DiCaprio has joined Instagram.
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