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People who are settled in the UK will be able to bring their Ukrainian immediate family members to join them, the prime minister has announced.
Boris Johnson said the UK would not "turn our backs in Ukraine's hour of need".
Speaking to a Ukrainian cathedral congregation, he said he had never seen "so clear a distinction between good and evil" as the conflict in Ukraine.
He later announced a further £40m of humanitarian aid for the country.
The government has been facing growing calls to waive visa rules for Ukrainians seeking sanctuary in the UK amid the ongoing Russian invasion.
Before the latest announcement, only those Ukrainians who were deemed to be "dependants" of those already in the UK were being guaranteed entry.
In his announcement, Mr Johnson said: "We want to be as generous as we possibly can, and certainly we want people who have relatives in Ukraine to be able to bring them over as fast as possible.
"We want to make sure that we have routes for people fleeing disaster, war, persecution in Ukraine to come here."
That statement came separately from his visit to the Cathedral of the Holy Family in London where he spoke a Ukrainian congregation, telling them the UK would do "everything it can to help economically, politically, diplomatically, militarily".