Putin, the 69-year-old Russian President, last week recognised the independence of two separatist regions in eastern Ukraine before launching the assault.
"This is a man that's completely unhinged," Luxon said.
"He's doing something that's unacceptable, a total affront to human rights, a total affront to democracy, a total affront to global peace and stability."
Yesterday Prime Minister Jacinda Ardern said expelling Russia's diplomats was one option on the table, but the Government had to consider the flow-on effects of that - it would almost certainly result in New Zealand's diplomats in Russia also being kicked out, leaving New Zealanders in the area with no direct consular help.
National's foreign affairs spokesman Gerry Brownlee said expelling Russia's ambassador to New Zealand would signal the idea that we don't want to be associated with the Russian Government.
"It's a very serious step," he said.
Yesterday, Russian and Ukrainian officials met on the war's fifth day, under the shadow of Putin's nuclear threats.
Moscow's invasion of Ukraine has encountered unexpectedly fierce resistance.
National's immigration spokeswoman Erica Stanford said the Government should create a special humanitarian visa for immediate relatives of Ukrainians who have settled in New Zealand.
"The situation in Ukraine is worsening by the day and Ukrainian Kiwis will be extremely worried about the safety of their family members back home," she said.
"This is something New Zealand can do now to support our Ukrainian Kiwis to bring their immediate family members here."
Stanford also said the Government should fast-track existing visa applications for Ukrainians, as Australia has done.
Yesterday, Foreign Affairs Minister Nanaia Mahuta issued a statement to the UN Human Rights Council.