Mr Albanese visited the towns of Bucha, Irpin and Hostomel on Sunday near the capital under very tight security, before meeting with Ukrainian President Volodymyr Zelenskiy in Kyiv.
In war-torn Irpin he described what he saw as "devastating".
"Here we have what; clearly a residential building," Mr Albanese said.
"Another one just behind it. Brutally assaulted. You know, this is a war crime."
Mr Albanese pledged to provide Ukraine with an additional 14 armoured personnel carriers, and 20 more Bushmaster vehicles and drones.
The $99.5 million boost is on top of a previously announced $285 million in military assistance, which included 40 Bushmasters and artillery pieces and $65 million in humanitarian assistance.
Australia's aid to Ukraine now totals about $390 million.
Mr Albanese also announced a ban on imports of Russian gold and sanctions and travel bans on 16 more Russian ministers and oligarchs, bringing the total number to 843 individuals and 62 entities targeted.
Meeting with Mr Zelenskiy, the prime minister reaffirmed Australia's support for Ukraine and promised to back the nation.
"I pay tribute to the courage, resilience, bravery and determination of you as the leader of Ukraine, of your defence force, but importantly as well of your entire population who are determined to stand up to a bully which is breaching international law without any provocation or any excuse," Mr Albanese said.
"Australia stands ready to continue to support the government and the people of Ukraine for as long as it takes for Ukraine to emerge victorious in defence of your national sovereignty and your homeland."
Mr Zelenskiy thanked his Australian counterpart for visiting and for the support.
"Our defenders highly appreciated, in particular, the Australian Bushmaster armoured personnel carriers and other specific assistance from Australia," he said.
"I am grateful to Australia for its firm, unyielding position on this issue."
Mr Zelenskiy said "Russia's aggressive potential" must be broken through stronger international cooperation.
He had addressed the Australian parliament in May, when he asked for further military support, saying Ukrainian forces needed Bushmasters.
Australia is the largest non-NATO contributor to the effort to support Ukraine, which was invaded by Russia in February.
Reuters cited a post by Kyiv Oblast Governor Oleksiy Kuleba on the messaging app Telegram confirming Mr Albanese had towns of Bucha, Irpin and Hostomel - places where Ukraine says has Russia committed war crimes against civilians who were buried in mass graves. Russia denies the allegations.
"Australia supports Ukraine and wants to see justice meted out for the crimes committed here," Mr Kuleba said.
Mr Albanese's trip to Kyiv followed an invitation in June from Ukraine's ambassador to Australia Vasyl Myroshnychenko.
"It's so important that the Australian prime minister could make this trip. It was not an easy one for him to make his logistics work," the ambassador told ABC radio on Monday.
"President Zelinskiy was extremely happy to see him."
Mr Myroshnychenko said Australia had been punching above its weight in terms of support, despite being so far away from Ukraine.
Last week, Mr Albanese said Australia was considering reopening its embassy in Ukraine.
Australian embassy staff have been working from neighbouring Poland since the war began.
Mr Albanese is expected to arrive back in Australia on Tuesday.
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