First Minster Alex Salmond confirmed the news at an international "climate justice" conference in Edinburgh.
The grant, of £3m, matches the previous amount from the Government's climate justice fund in 2012. That money was used to support water projects in Malawi and Zambia, and comes after a recent IPCC report highlighting the impact of climate change.
Minister Salmond said: "We are taking practical action on the ground to help those most vulnerable to climate change – those in the world's poorest communities in countries like Malawi – Scotland's historic sister nation.
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"By doubling the Climate Justice Fund we can provide genuine life-saving and life changing help to those communities.
"The Scottish Government has been at the forefront of the fight against climate change, such as our ambitious emissions reduction and renewables targets."
The additional funds have been welcomed by environmental campaigners.
Chris Hegarty, Chair of the Enough Food for Everyone IF Scotland campaign, explained: "The Scottish Government's announcement today to increase its Climate Justice Fund is a major victory for supporters of the Enough Food for Everyone IF campaign in Scotland.
"It is an important step along the road to Scotland repaying its climate debt to the poorer countries, and a timely example to other nations who should follow suit."
Tom Ballantine, Chair of the Stop Climate Chaos Scotland coalition, added: "It is great to see Scotland setting a positive example to other wealthy nations by reconfirming its commitment to the Climate Justice Fund with the additional money announced today.
"This will enable Scotland to provide urgently needed support to people living in poverty in developing countries who are already struggling to plant and harvest their crops in the face of increasingly unpredictable and extreme weather."
(JP/CD)
