A cathedral at one of the holiest sites in eastern Orthodox Christianity burned on Monday after Russia attacked Kyiv in a massive, overnight volley of missiles and drones.

Explosions shook buildings in Kyiv through the night, killing four and injuring 25 people. At least four residential buildings were hit, a local emergency service said. Russia has intensified missile attacks on Ukraine’s capital amid setbacks on the battlefield in eastern Ukraine.

The cathedral that was struck, the Dormitian Cathedral, is at the site of the Pechersk monastery. The monastery is one of the oldest and holiest places for both the Ukrainian and the Russian Orthodox churches, and it holds importance in the early history of both countries. No injuries were reported at the site.

Medieval catacombs hold the mummies of early Slavic saints, and church buildings or elements of them date back more than 1,000 years.

The cathedral’s roof was engulfed in flames, as seen in photographs released by the Orthodox Church of Ukraine. Images also showed flames and smoke rising beside the onion dome cupolas.

Kyiv’s mayor, Vitali Klitschko, and the military governor of Kyiv, Timur Tkachenko, confirmed the damage.

“Damage on the territory of the monastery is significant, and there is a serious fire,” Mr. Tkachenko wrote.

A religious leader at the monastery, Bishop Avraamii, posted on Facebook that priests and monks had managed to remove holy items including old icons from the cathedral.

“First of all, we organized the evacuation of holy and liturgical items, ancient icons” of religious and historical value, Bishop Avraamii wrote.

Elsewhere in Ukraine, authorities in the eastern city of Kharkiv said five rescue personnel were killed and at least five others injured in a secondary attack on a site damaged by drones or missiles earlier Monday. Such double strikes are usually intended to hit rescue workers.