The overnight attack mostly targeted western regions of the country, the air force said on Thursday, where much of the military aid provided by Ukraine's Western allies is believed to be delivered and stored.
The strikes killed at least one person and injured 15 others, according to officials.
It was Russia's third largest aerial attack in 2025 in terms of the number of drones fired and the eighth-largest in terms of missiles, according to official figures.
The strikes occurred during a renewed US-led effort to reach a peace settlement following Russia's February 2022 invasion of its neighbour.
US President Donald Trump discussed the war with Russian President Vladimir Putin in Alaska last week, and at the start of this week hosted Ukrainian President Volodymyr Zelenskiy and European leaders at the White House.
Russia has fired nearly 1000 long-range drones and missiles at Ukraine since the White House talks.
Ukraine and European leaders have accused Putin of stalling in ongoing peace efforts, including Ukraine's proposal of a ceasefire and Zelenskiy's offer to sit down with the Russian leader.
The Kremlin has reacted coolly to those possibilities.
Zelenskiy condemned the overnight attack, saying it was carried out "as if nothing were changing at all".
Moscow had shown no signs of pursuing meaningful negotiations to end the war, Zelenskiy said.
He urged the international community to respond with stronger pressure on Moscow, including tougher sanctions and tariffs.
Ukraine, meanwhile, has kept up its attacks with domestically produced long-range drones on infrastructure inside Russia that supports Moscow's war effort.
Among other targets, it has hit oil refineries, and Russian wholesale petrol prices have reached record highs in recent days.
Almost all the overnight missiles were fired from inside Russia, and reached deep into western Ukraine.
Western parts of Ukraine are far from the battlefield's front line in the east and south of the country, where a grinding war of attrition has killed tens of thousands of soldiers on both sides.
In the western city of Lviv, one person was killed and three were injured as the attack damaged 26 residential buildings, a kindergarten and administrative buildings, regional head Maksym Kozytskyi wrote on Telegram.
Ukraine's Foreign Minister Andrii Sybiha said Russia struck a "major American electronics manufacturer" in western Ukraine, which Zelenskiy said produced domestic appliances.
In comments on Wednesday that were embargoed until Thursday, Zelenskiy said Ukraine would hold intensive meetings to understand what kind of security guarantees its allies were willing to provide.
The details are being hammered out by national security advisers and military officials.
The plans would become clearer within 10 days, Zelenskiy said.
He then expects to be ready to hold direct talks with Putin for the first time since the full-scale invasion.
The talks could also be conducted in a trilateral format alongside Trump, Zelenskiy said.
A venue for the meeting was being discussed, and Switzerland, Austria and Turkey were possibilities, Zelenskiy said.
Russian Foreign Minister Sergey Lavrov said on Wednesday that working on security arrangements in Ukraine without Moscow's involvement was not feasible, according to state news agency RIA Novosti.
Zelenskiy said that in his meeting with Trump in the Oval Office on Monday he sought to convince the American president that the battlefield situation was not as bad for Ukraine as Putin portrayed.
Zelenskiy pointed to errors in the US map of the front line that he said showed Russia holding more territory than it actually did.
