The Spanish royal couple was joined by their daughters, Princess Leonor, 20, and Infanta Sofia, 19, for the official welcome ceremony outside the Royal Palace in Madrid on Saturday.
Letizia, 53, even performed a rare double curtsy for the Pontiff, though traditionally, monarchs would kneel before him.
The Pope is making an apostolic journey to Spain from 6 to 12 June, marking the first papal visit to the country since Benedict XVI visited in 2011.
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Starting in Madrid, he will also visit Barcelona and the Canary Islands of Gran Canaria and Tenerife. Pope Leo XIV became Pope on 8 May, 2025, following the passing of Pope Francis.
Letizia formally welcomed the Pontiff with a rare double curtsy – one before getting into the car and a second upon arrival at the Royal Palace, where Leonor and Sofia were waiting.
Pope Leo landed on an Italian Airways A320 NEO aircraft after travelling from Rome to Adolfo Suárez-Madrid Barajas Airport.
The Pope said: "Personally, I am very happy to be making this trip. I have come to Spain many times, but this is my first time on this mission of fulfilling an apostolic visit, meeting the faithful, celebrating the faith, and greeting all of society, because the Church has a message for everyone."
Pope Leo boarded the plane wearing a white cassock, but upon descending the steps in Madrid, he changed into a crimson mozzetta (white is worn only at Easter) over which he wore his pectoral cross. On his head, as always, he wore the zucchetto, a round white silk cap.
Many of his planned engagements centre on issues around marginalised people, youth, and migrants, alongside meetings with the Spanish royals, government figures, and church officials.
A highlight of the itinerary sees Pope Leo inaugurate the recently completed Tower of Jesus Christ spire at the Basílica de la Sagrada Familia in Barcelona, to coincide with the 100th anniversary of the architect Antoni Gaudí's death.
Why was Queen Letizia allowed to wear white, but Princess Leonor and Infanta Sofia wore black?
Letizia is one of the few royal women allowed to wear white to meet the Pope, as she is Queen of a Catholic country. Other women granted the honour include Queen Mathilde of Belgium, Princess Charlene of Monaco, Princess Marina of Naples, and Grand Duchess Stephanie of Luxembourg.
Queen Letizia wore white, but her daughters were seen in black
Two former queens, Queen Paolo of Belgium and Queen Sofia of Spain, are also allowed to wear white. Usually, the look is also accompanied by a lace mantilla.
This means wearing white in front of the Pope is very rare. Usually, royal women would wear black, as Princess Leonor and Infanta Sofia did on Saturday.
Queen Camilla previously dressed in a black dress and veil to meet the new Pope in October 2025.
Queen Letizia and King Felipe of Spain visited the Vatican on Friday, and enjoyed a 50-minute private audience with Pope Leo XIV at the Apostolic Palace
King Felipe VI and Queen Letizia of Spain's 20-year-old daughter, completed her Basic Parachuting Course at the Mendez Parada Military School of Parachuting