To a standing ovation from parliamentarians and the viewing gallery, the defiant president appeared via videolink and proclaimed Russia's aggression as a real threat to Australia.
"That is the nature of evil - it can instantly cross any distance, any barriers, destroy lives," he said.
"Unpunished evil comes back with inspiration and a feeling of almightiness."
Mr Zelenskiy said the invasion of his country wouldn't have happened if Russia was held accountable for the shooting down of MH17 in 2014.
"We have to correct some horrible mistakes and correct them now," he said.
"We need new sanctions against Russia until they stop blackmailing other countries with their nuclear missiles. They have to pay the highest price."
The Ukrainian president asked for access to Australian military vehicles like the Bushmaster to help the country defend its territory.
"That could help Ukraine significantly - we would be very grateful if you could share those with us," he said.
Mr Zelenskiy also invited Australia to help with the restoration of the country's coastal cities.
"The geographical distance between us is huge, but what does this distance mean for those who have a common understanding?
"Geography doesn't matter."
Prime Minister Scott Morrison used his opening remarks to announce a further $25 million of defensive military equipment for Ukraine and to brand Russian President Vladimir Putin as the "war criminal of Moscow".
The package includes tactical decoys, unmanned aerial and ground systems, rations and medical supplies.
"Ukraine and Australia are separated by half the earth. Our languages, accents, histories and cultures are different but we share an affinity for democracy or freedom," Mr Morrison told the president and the parliament.
"Mr President, you have our praise. But you also have our weapons, our humanitarian aid, our sanctions against those who seek to deny your freedom."
Mr Morrison also pledged to help Ukraine rebuild following the war, praising the "strong people of an indomitable country".
Opposition Leader Anthony Albanese likened Russia's invasion to the devastation wrought by Hitler in World War II, saying Putin's aggression was prefaced by a "poisonous, nationalistic lie".
"As you stand up to this latest tyrant, you are showing us what true courage is," Mr Albanese said.
"It is the courage that is embodied by you (President Zelenskiy). You are fighting for your country and your people."
The government's aid package was announced alongside an additional 35 per cent tariff for all imports coming from Russia and Belarus on top of general duties that already apply.
The tax hike will come into effect from April 25 alongside a prohibition on Russian oil and energy products.
Australia has also granted almost 5600 visas for people in Ukraine, more than 1400 of whom have since arrived.
It comes as a top United Kingdom intelligence official told the National Security College in Canberra that the Russian president has misjudged the resistance of the Ukrainian people, with Russian soldiers losing morale and refusing to follow orders.
"(Vladimir Putin) over-estimated the abilities of his military to secure a rapid victory," Sir Jeremy Fleming said.
"We've seen Russian soldiers - short of weapons and morale - refusing to carry out orders, sabotaging their own equipment and even accidentally shooting down their own aircraft."
Australia is providing $91 million in military assistance, $65 million in humanitarian assistance and 70,000 tonnes of thermal coal to meet Ukraine's energy needs, as well as temporary protection visas and support for Ukrainian community groups in Australia.
There are also targeted sanctions on individuals and entities, the prohibition of energy, oil and gas products from Russia, and a ban on exports of alumina and bauxite to Russia.
with Reuters
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