In a primetime speech, Mr Biden vowed "an unwavering resolve that freedom will always triumph over tyranny".
His State of the Union speech comes as pandemic-weary Americans grapple with galloping inflation.
Mr Biden is almost as unpopular as Donald Trump at this point in his presidency.
The Democratic president told lawmakers on Tuesday night: "Putin's war was premeditated and unprovoked. He rejected repeated efforts at diplomacy.
"He thought the West and Nato wouldn't respond. And, he thought he could divide us here at home.
"Putin was wrong. We were ready."
Mr Biden announced that the US would ban Russian aircraft from American airspace, following similar bans by Canadian and European authorities.
Vowing further economic retaliation against Russia, the US president said of Mr Putin: "He has no idea what's coming."
The US president also welcomed Ukrainian Ambassador Oksana Markarova, who was sitting in US First Lady Jill Biden's VIP box for the event.
Meanwhile, five people have died after Russia attacked a TV tower in Kyiv, hitting nearby broadcast facilities, Ukrainian officials say.
It comes after Russia warned residents that it was preparing to hit targets in the Ukrainian capital.
It's unclear whether the tower itself was directly hit - it remains standing - but the blasts took some broadcasts off air.