The royal purification ablution bath as part of his coronation ceremony at the Grand Palace in Bangkok.
Slightly more than five hours after starting the day-into-night, 7.15-kilometre journey, the king reached the last of three prominent Buddhist temples - the Temple of the Reclining Buddha - where he stopped to pay homage to Buddha images.
Tens of thousands of well-wishers brandishing both Thai and royal flags and wearing yellow - a color associated with the monarch - lined the route for the rare spectacle.
His father, King Bhumibol Adulyadej, died in 2016; Vajiralongkorn's coronation was originally held off because of the official mourning period, though no reason was given for the extended delay. In his first speech earlier on Saturday to members of the royal family, the Privy Council, and top government officials, among others, the king called for national unity.
Suthida does not have the same royal lineage as Vajiralongkorn's mother Queen Sirikit, who is the great-granddaughter of the Chakri dynasty's fifth king.
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King Vajiralongkorn, who has reportedly been Queen Suthida's romantic partner for many years, has been married and divorced three times in the past.
At least 150,000 people from all over the country were expected to greet their newly crowned king, first during a parade around old Bangkok on Sunday, then near the Grand Palace where the king will appear on the balcony on Monday.
He also delivered his first royal command as King, saying, "I shall continue, preserve, and build upon the royal legacy and shall reign with righteousness for the benefit and happiness of the people forever".
The main ceremony will take place on Saturday, when Vajiralongkorn will put on a crown, more than 200 years old, 66 centimeters (26 inches) high, weighing 7.3 kilograms (16 pounds) and ornamented with diamonds set in gold enamel.
One of the family members to receive royal titles was 14-year-old Prince Dipangkorn Rasmijoti, who knelt and prostrated in front of his father as he was anointed with water.
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More than 1,300 personnel were in the procession.
"Because King Mongkut was a monk, he ordered that the procession should visit important Buddhist temples so the new monarch can provide alms to monks", said Tongthong Chandransu, an expert on Thai royal rituals.
As an only son, he was destined to rule from the moment he entered the world and was born in 1952, a time when Thailand's constitutional monarchy flourished, under his father. Thailand's monarchy is swaddled in ritual, protocol and hierarchy all orbiting around the king, who is viewed as a demigod.
He received his crown on Saturday in a mixed Buddhist-Hindu ceremony, which was televised live on all channels across the country, amid the splendor of Bangkok's Golden Palace.
"When the auspicious time arrived, the royal astrologer hit the Gong of Victory, the scribe and the royal augur began inscribing on the Royal Golden Plaques the official title of the King and the King's Horoscope".
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The junta that seized power in 2014 and has vowed to defend the monarchy is aiming to return to power through the ballot box.