The New Zealand Defence Force (NZDF) will begin to deploy up to 120 additional personnel to the UK to train Ukrainian infantry recruits.
Over the next three weeks, the deployment will see an infantry training contingent, drawn from the NZDF, split into two teams to train approximately 800 Ukrainian Armed Forces personnel.
This deployment until 30 November follows their completed deployment of 30 NZDF personnel in May.
New Zealand Prime Minister Jacinda Ardern, Defence Minister Peeni Henare, and Chief of Defence Air Marshal Kevin Short announced the move after their weekly Cabinet meeting.
"New Zealand has been clear that we will continue to answer the call of Ukraine for practical support as they defend their homeland and people against Russia's unjustified invasion," Prime Minister Ardern said.
Air Marshal Short said the Cabinet decision follows an invitation from the UK Armed Forces for the NZDF to contribute to the infantry training programme.
"I am very pleased that this deployment has been approved, particularly for the Army, as it provides an opportunity for some of our people to contribute further in a very meaningful way as we respond to a request from a close partner," Air Marshal Kevin Short said.
"Our contribution through earlier efforts have already helped and this decision continues our aid to Ukraine as it defends itself against Russia's unjustified and illegal invasion."
He added: "The deployment is a good indication of the high regard our partners have for our professionalism as a military force."
The contingent of New Zealand personnel will travel on civilian flights to the UK and will begin their work to equip Ukrainian recruits with the core skills to be effective in frontline combat, deployed until 30 November.
The training is based on the basic UK soldier course, which includes weapon handling, combat first aid, operational law and other soldier skills.
The statement said no NZDF personnel will enter Ukraine during the deployment, which will be based at Ministry of Defence (MOD) sites across the UK.
The first cohort of Ukrainian troops came to the end of their training in the UK in mid-July.
Watch: Ben Wallace in July visited Ukrainian troops training in the UK.
Defence Secretary Ben Wallace told MPs in the Commons that it has been a "learning experience for both sides".
The Ukrainian recruits are part of the Government's commitment to training 10,000 troops every 120 days.
About 1,000 UK service personnel are deployed to run the programme.