The prime minister met with Mr â� Zelenskiy on the sidelines of the United Nations General Assembly in New York on Thursday, Australian time, pledging $60 million more in support for Ukraine's fight against Russia's invasion.
The 10-year bilateral security agreement, signed by both leaders, will lead to an extra $45 million in Australian Defence Force equipment for Ukraine.
A further $10 million will go to Ukraine's energy support fund, while $5 million will be spent on humanitarian assistance.
The $60 million fund will bring Australia's total contribution to Ukraine since Russia's invasion in 2022 to $1.9 billion.
The prime minister became emotional as he paid tribute to his "friend" Mr Zelenskiy in his fight against Russian aggression.
"(Mr Zelenskiy's) leadership has been ... quite extraordinary, leading people in circumstances which are extraordinarily difficult," he said.
Mr Albanese said the agreement was a proud day for Australians in seeking to uphold international laws.
"This is an issue not just for Europe, this is an issue for the world," he told reporters in New York upon signing the agreement.
"If a large, more powerful country in Russia is allowed to profit from breaking the international rules of law with its illegal and immoral invasion of Ukraine, then that sets a bad precedent for the entire world."
"Russia thought it could just steamroll through in a matter of weeks, and what we have found is that the people of Ukraine were underestimated."
The two leaders hugged when they first met in-person at the summit, with Mr Zelenskiy thanking Australia for its support to Ukraine throughout the conflict.
"(The agreement is) the strongest document between our countries," he told reporters.
"We really will increase our co-production and trade and, of course, security, which is really important.
"It's all for our people, for the security."
Mr Albanese said the bilateral agreement would be in place not only during the war in Ukraine, but during peacetime once the conflict concludes.
As part of the agreement, Australia will also step up training to help Ukrainian forces deter and repel any future Russian attacks.
It will also look to explore co-operation for training centres and jointly produce air-defence measures, missiles and drones.
Australia will join forces with the United Kingdom and Norway-led coalition to help support the development of Ukraine's navy.
Work will be carried out to strengthen Ukraine's maritime capability.
Australia and Ukraine will also work together to rebuilding infrastructure such as military healthcare facilities and training centres.
Extra sanctions have also been imposed on Russia, coinciding with the announcement of the agreement.
It brings the total sanctions placed on Russia and its supporters by the federal government to more than 1900.
The announcement of the security pact came on the same day it was revealed the US would invite Russian President Vladimir Putin to attend the G20 summit.
The summit will take place in Florida in December at the Trump National Golf Club.
While Russia remains a member of the G20, Mr Putin has not attended in person since its invasion of Ukraine in 2022.
Russia has often been represented by Foreign Minister Sergei Lavrov.
Russia has not responded to the invitation.
Mr Albanese said he had no plans of interacting with Mr Putin at the summit.
"I have no intention of having discussions with Mr Putin, I think that his actions have been reprehensible," he said.
"What I'm responsible for is Australia's view, and Australia's view is very clear, which is Mr Putin would not be welcome in Australia."
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