The house of Zedguinidze-Amilakhvari had formerly served as hereditary Master of the Horse to the Georgian Crown (Amilakhvari) and retained their princely dignity during the Imperial Russian rule of Georgia.
Villiers was Knight Marshal to the royal household in succession to his father; Master of the Horse to Queen Mary; and Lord Chamberlain to William III and Queen Anne.
On his return from the continent, he did well at the Royal Court, as a descendent of George, Duke of Clarence, brother of King Edward IV, seemed to assure him and he was appointed Master of the Horse in 1760.
He served as Master of the Horse from 1806 to 1807 in the Ministry of All the Talents headed by Lord Grenville.
On 2 September 2006 he married Nina Vestey, a niece of the 3rd Baron Vestey, Master of the Horse.
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These women included Lady Elizabeth Boleyn; Queen Anne's aunt, Lady Anne Shelton; Lady Mary Kingston, the wife of Sir William Kingston, the Lieutenant of the Tower; Lady Margaret Coffin, the wife of Queen Anne's Master of the Horse; and Elizabeth Stoner, wife of the King's Serjeant-at-Arms.
In 1701, she married Johann Adolf, Baron von Kielmansegg (1668–1717), Deputy Master of the Horse to George Louis and they had three sons and two daughters, the eldest of whom, Charlotte (1703–1782), married Emanuel Howe, 2nd Viscount Howe.
Many other well known equestrians belong to its number including Captain Mark Phillips CVO and Samuel Vestey (Master of the Horse).
As early as 288-301, the Bagratid prince Smbat held the hereditary Armenian titles of Aspet, which means Master of the Horse, and T'agatir, which means Coronant of the King.
John Cheyne, Baron Cheyne (1445–1499), Master of the Horse to Edward IV of England
In the latter year, he was appointed Master of the Horse to Catherine of Braganza, whose Treasurer he later became in 1684.