All of Ukraine has been put on alert after multiple explosions occurred in Kiev and Russia launched a series of airstrikes.
Poland announced that it had deployed its air force to ensure the security of Polish airspace after attacks also targeted the Ukrainian border region of Lviv.
The attack began at 05:00 (03:00 GMT) in the capital.
Ukraine's military said its air defense systems were engaged in repelling the attack.
Kiev Military Executive Chief Serhiy Popko said about a dozen Russian missiles were destroyed in the skies over the capital and its suburbs.
There were no reports of casualties or major damage from the attack, he added in a statement on Telegram.
Lviv Mayor Andriy Sadovy said on Telegram that the city itself was not affected. However, around 20 missiles and seven attack drones were fired over a wide area of the Lviv region, targeting “critical infrastructure.”
Ukraine had previously been placed on national alert, warning of cruise missile launches from Russian strategic bombers.
Meanwhile, the Polish Military Operations Command (RSZ) said: “Polish and allied aircraft have been activated.
“All necessary procedures to ensure the safety of Polish airspace have been activated and RSZ is continuously monitoring the situation,” it added.
Residents of Kiev were photographed taking shelter in a metro station.
Moscow has not yet commented on Sunday's attack.
The Russian-installed governor of annexed Crimea's Sevastopol port announced late Saturday that Russian forces shot down 10 Ukrainian missiles over the city.
Mikhail Razvozhaev said on Telegram that an office building and gas pipes were destroyed and a woman was injured by shrapnel.