He was pictured assisting the homeless as they waited to receive the vaccine in a video released by the Vatican.
Vatican News reported that one man who received the vaccine, identified as Mario, said that he felt he now had “extra security.”
“We thank the pope for this gift,” he said.
Vatican News said that the vaccine recipients were residents of the Palazzo Migliori, a 19th-century palace converted into a homeless shelter, and two houses near the Vatican run by Mother Teresa’s Missionaries of Charity. It added that the men and women, from Italy, Georgia, and Romania, were aged 60 and over.
The Holy See press office said that further groups of homeless people would receive the vaccine in the coming days.
Pope Francis, 84, and Pope emeritus Benedict XVI, 93, received their first dose of the COVID-19 vaccine last week.
The Vatican began administering vaccinations against COVID-19 on Jan. 13.
Vatican residents and employees and their families are receiving doses of the Pfizer-BioNtech vaccine.
Vatican City State, the world’s smallest independent nation-state, has a population of around 800 people. But together with the Holy See, the sovereign entity that predates it, it employs more than 4,000 people.
Since the beginning of the coronavirus outbreak, a total of 27 people have tested positive for COVID-19 in Vatican City State. Among them were at least 11 members of the Swiss Guard.
Dr. Andrea Arcangeli, head of the Vatican health service, said on Jan. 2 that the Vatican had purchased a low-temperature refrigerator to store the vaccine.
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“Priority will be given to health and public safety personnel, to the elderly and to personnel most frequently in contact with the public,” he said.
At his traditional Christmas “Urbi et Orbi” blessing, the pope called for COVID-19 vaccines to be made available to the world’s neediest people.
He said: “I ask everyone -- government leaders, businesses, international organizations -- to foster cooperation and not competition, and to seek a solution for everyone: vaccines for all, especially for the most vulnerable and needy of all regions of the planet. Before all others: the most vulnerable and needy!”