Charles arrived in the Romanian capital on the same day British Prime Minister Theresa May launched the Brexit process.
President Klaus Iohannis greeted the prince at the 17th-century Cotroceni presidential palace and will give him the Order of the Star of Romania, an award for exceptional service to Romania.
Charles' website said his tour would "highlight the UK's relationship with European partners in areas including social cohesion, military ties and combatting human trafficking."
He leaves Romania on Friday and will then travel to Italy on a tour that is seen as a European charm offensive to cement ties and promote military ties and combat human trafficking.
Charles' wife, Camilla, is expected to accompany him to Italy and Austria.
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