Five defence force personnel from the 16th Field Regiment are already on their way to the United Kingdom to help train Ukrainian troops, with another 25 to follow early next week.
They will be training Ukrainian military personnel on how to operate L119 105mm light field guns.
The government announced the support on Monday - each round of training will take a week, with the New Zealand team asked to help until the end of July.
Commanding officer Lieutenant Colonel Dean Gerling said the soldiers had a range of experience.
They will teach Ukrainian forces to use the 40 gun sights New Zealand is giving them, along with a small amount of ammunition to help with training.
"From the gunner rank, so the lowest rank within 16th Field Regiment, up until major, so one of the battery commanders.
"They've all spent the last couple of days practicing, rehearsing method of instruction on dial sights, how to use it properly and make sure things are working."
New Zealand's forces no longer used the tools, with modern methods like GPS finding more favour.
"The dial sights themselves were replaced approximately eight years ago, but we have kept training in that as a means of revisionary method," Lieutenant Colonel Gerling said.
"The technology we use now uses GPS and gyros to make sure we know where we are on earth and where we're pointing in direction as well."
NZDF is going to train Ukrainian soldiers in UK to use the L119 gun. Photo: Supplied / NZDF
The commander said one of the reasons for the quick deployment was the language barrier.
The New Zealand force needed to make sure the interpreters understood the technical side of gunnery so they could translate this for the Ukrainian soldiers, he said.
Meanwhile, the soldiers were "really excited" to be heading overseas.
"When we started looking at this, a number of hands went up across the regiment of wanting to deploy," Lieutenant Colonel Gerling said.
"Really excited amongst the unit with questions of can we send more, are we going to do more?"
The government previously approved the deployment of defence personnel to the UK, to help with international support for Ukraine's defence, but it hasn't been without controversy - some former Labour Party figures say New Zealand has effectively gone to war without consulting the public.