Ministers meeting in Brussels are expected to agree to deploy British troops to help train the Malian army.
An EU training mission is likely to see "tens" of troops sent in a "support" role to the north African state.
A separate meeting in Africa is likely to see a number of personnel offered to support a United Nations training mission in areas neighbouring Mali.
The Ministry of Defence refused to confirm that up to 200 troops could be involved in the missions.
David Cameron told French President Francois Hollande at the weekend that Britain is "keen" to help Paris with its military operation to oust Islamist militants in northern Mali.
The Prime Minister has said the UK is ready to offer logistical, intelligence and surveillance help to France but has ruled out a combat role for British personnel.
The RAF has already provided two heavy-lift C-17 transport planes and a Sentinel surveillance aircraft to assist France's operation.
Former head of the Army General Sir Mike Jackson backed the Government's position but warned that nations involved may face a "protracted guerrilla warfare".
"It doesn't really surprise me that the British Government feels it needs to be seen to be helping," he said. "We cannot let states fail because we know from recent history that failed states just lead to really difficult circumstances, instability."
He added: "What Mali and France, and indeed other countries who may choose to assist may face, of course, is a protracted guerrilla warfare taking place away from the conurbations."
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