Senator Payne said she had been in contact with her Ukrainian counterpart and indicated Australia would be prepared to consider any calls for help, but no formal requests have been made.
"To be clear, that is not about direct military support. That is not on the table from Australia's perspective," she told reporters on Friday following talks with her British counterpart.
"But we will work closely with Ukraine in the coming days and weeks in terms of challenges that they are dealing with and continue to affirm our views on their sovereignty and territorial integrity."
Australia's ambassador to Ukraine, Bruce Edwards, has said the country would be prepared to use additional autonomous sanctions if warranted.
UK Foreign Secretary Elizabeth Truss said Australia and Britain would be united in their response.
"We have been exploring how we can make even more of this great partnership to protect our people, our partners, and our freedoms," she said following a meeting which also included the defence ministers from both countries.
"The price of liberty is eternal vigilance."
Ms Truss used a keynote address to the Lowy Institute on Friday afternoon to deliver a strong message to Russia over the threats to Ukrainian sovereignty.
She urged Russian President Vladimir Putin to "desist and step back from Ukraine before (making) a massive strategic mistake".
"The Kremlin has not learned the lessons of history. Invasion will only lead to a terrible quagmire and loss of life," she said.
The foreign secretary said any incursion would be met by resistance from Ukraine and serious economic sanctions from the West, but stopped short of committing troops.
"We have been clear there will be severe consequences should Vladimir Putin stage an incursion into Ukraine," Ms Truss said.
"Economic consequences in particular that would have a very damaging effect.
"Ukraine isn't a member of NATO so it's not in the same position as the Baltic states where there would be direct action in the case of any conflict."
Ms Truss also outlined how closer defence, cyber and economic ties to Australia will help counter Russian and Chinese aggression but admitted the world had not done enough to deter aggression since the end of the Cold War.
"What happens in eastern Europe matters for the world," she said.
Senator Payne said the relationship between Australia and the UK was vital in today's "complex and fractious strategic environment in which authoritarian regimes are behaving as though now is their time to increase oppression internally and coerce others internationally".
"We are faced with coercion, disinformation, cyber attacks, with a disregard for the rules and norms that have given us decades of peace and stability, regularly," she told the Lowy Institute.
Senator Payne said Australia and the UK were "primed" to defend their values and principles, be it against China in the South China Sea or Russia on the Ukrainian border.
Ms Truss said the world needed to work together to reduce economic dependence on Russia, as it faces emboldened aggression at levels not seen since the Cold War.
"Threats to freedom, democracy and the rule of law are not just regional – they're global. And so we must respond together," she urged.
"We are very ready to act in the immediate term, but in the longer term this is why it's so important that we are investing in developing countries, we are trading right across the world."
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