Alongside her husband William Hoapili Kaʻauwai, she traveled with Queen Emma of Hawaii to Europe between 1865 and 1866, and circumnavigated the globe upon their return eastward via New Zealand.

Kiliwehi was born c. 1840,[1] as the daughter of Kuini Liliha, an influential high chiefess and Governor of Oahu, and Haʻalou (different from the chief executed for adultery with one of Kamehameha II's wives in 1822).

[2] Kiliwehi was also the name of an early Hawaiian high chiefess who was the daughter of King Kamehameha I and Peleuli, the wife of Prime Minister Kalanimoku and the mother of Leleiohoku I.

[3] She had many half-siblings including sisters: Jane Loeau (1828–1873), Abigail Maheha (1832–1861), and Kailinoa, and brothers: Pius F. Koakanu (died 1880) and Aberahama Kaikioewa Palekaluhi (1830–1912).

[4] Kiliwehi and her sister Abigail Maheha were adopted under the Hawaiian tradition of hānai by the Princess Kekauʻōnohi, a granddaughter of Kamehameha I who served as Governor of Kauai.

[7] Kiliwehi married William Hoapili Kaʻauwai (1835–1874), a Maui high chief, politician and the only ordained Native Hawaiian priest of the Anglican Church of Hawaii.

[8] After Kamehameha IV's death, Queen Emma decided to travel to England to solicit donations for erecting a cathedral in Honolulu and to continue the legacy of her husband.

In her private journal, Victoria mentioned Kiliwehi as "Mrs. Hoopile", writing that Queen Emma "presented her lady, whose husband is her Chaplain, both being Hawaiians".

They returned to London and took an extended route back to Hawaii, stopping off in Auckland, New Zealand without the knowledge or permission of Queen Emma or King Kamehameha V. Prior to leaving England, Kaʻauwai had written to the Hawaiian Minister of Finance Charles Coffin Harris indicating they intended to take a "rather long round-about, and slow way toward home".

Her husband later had an illegitimate son William Hoapili Kaʻauwai II, whose mother is either mentioned as Keanolani or Keauookalau, the wife of Lihilihi, of Kauai.