The Canada international left back is the first professional footballer to be entrusted with such a position.
Davies was born at the Buduburam refugee camp in Ghana after his parents fled the Liberian civil war at the turn of the century. They relocated to Canada when Davies was five years old.
The 20-year-old joined Bayern Munich from Major League Soccer outfit Vancouver Whitecaps in January 2019 and has since developed into one of Europe’s most enterprising left backs, winning two Bundesliga titles, the UEFA Champions League and a host of other trophies.
Davies told the agency's website: "I am proud to join the UN Refugee Agency as a goodwill ambassador. My own experiences make me want to speak up for refugees, to share their stories and to help make a difference.
"Whilst the refugee camp provided a safe place for my family when they fled war, I often wonder where I would have been if I had stayed there and not benefited from the opportunities I got thanks to resettlement.
"I don't think I would have made it to where I am today. I want people to know about the importance of helping refugees, wherever they are, in camps or cities, in neighbouring countries or countries of resettlement such as Canada.
"Refugees need our support to survive, but also access to education and sports, so they can fulfil their potential and truly thrive."
UNHCR head Filippo Grandi added: "Alphonso personifies the power of sport and we are truly honoured to have him joining us.
"Sport has the incredible power to bring hope, to heal and to help shape the future for those forced to flee. In our work with refugees, we see daily what uplifting difference sports can make in their lives.
"His personal story, his talent and triumph as a professional footballer and his commitment to help refugees is impressive. I am looking forward to working with him."
