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The Prime Minister said he hoped Britain's action would "break the log jam" and make an international agreement on banning the weapons possible.
He was speaking as talks reached their final stages in Irish capital Dublin on prohibiting the use of the weapons, which have been blamed for killing and maiming thousands of civilians in war zones.
Speaking in 10 Downing Street, Mr Brown said: "We have decided, after a great deal of discussion, that we can help break the log jam so that we can get international agreement that would ban cluster bombs.
"We have decided we will take all our types of cluster bombs out of service. I believe that is going to make a difference to the negotiations that are now taking place.
"I look forward to other countries following us in this action and I look forward to other countries being able to take these cluster bombs out of service.
"I think this would be a big step forward to make the world a safer place."