Ireland's Defence Minister Alan Shatter confirmed eight Irish soldiers and 18 from the UK will travel to the troubled African country with the Royal Irish Regiment.
UTV learned last month of the possible RIR deployment.
The joint operation will be led by the British and will be part of an overall European Union military training mission (EUTM). Around 200 soldiers from across the EU will be deployed next month.
French and Malian troops are battling to regain control of the north of the country from Islamist rebels.
Training is expected to begin in April and will provide the Malian armed forces with military training and advice on improving and maintaining security in the country and restoring the authority of its government.
Mr Shatter said: "This will be the first occasion there has been a formal joint deployment under the UN mandate of mission involving our defence forces and the UK."
He confirmed the mission after bilateral talks with the UK's international security strategy minister Andrew Murrison in Dublin, where European defence ministers are holding an informal meeting as part as Ireland's presidency of the EU.
It will include armed military training as well as human rights issues and the protection of civilians.
Mr Shatter said the military co-operation, almost two years after the Queen's historic visit to Ireland, was a further sign of closer ties between the two nations.
"We would see this as yet another step along the road of the development and continuing broadening and enhancing of relationships with the United Kingdom," he added.
Mr Shatter said while Ireland and UK forces have worked together in the past - including on UN Blue Hat, EU-led and Nato-led operations in the Balkans and Afghanistan - this is the first joint military contingent and would involve peacekeeping, training and tackling human rights abuses.
He also revealed the defence ministers did not have detailed discussions on whether the conflict in Mali had caused any extra terrorist threats on Europe.
"There is a consciousness that some of the fundamentalists and jihadi groups do pose a threat in a European context, but there's nothing new about that," added Mr Shatter.
Last month, Prime Minister David Cameron confirmed the government's cooperation in Mali while he was visiting the neighbouring north African country of Algeria, in the wake of the hostage crisis at a gas field there.
Islamist militants kidnapped 135 oil rig workers, including Belfast man Stephen McFaul, who later escaped.
Mr Cameron said his aim was to help the country "help itself" amid a growing threat from al Qaida-linked terrorists.
"The In Amenas attack and the situation in Mali reminds us of the importance of partnership between Britain and countries in the region," he told journalists.