Kiliwehi married William Hoapili Kaʻauwai, a Maui high chief, politician and the only ordained Native Hawaiian priest of the Anglican Church of Hawaii. They had no children. She and her husband became associated with King Kamehameha IV and his wife Queen Emma. They became early converts to the Anglican faith. 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. She chose Kiliwehi as her lady-in-waiting and her husband Kaʻauwai to be her chaplain to accompany her on this trip from 1865 to 1866. They traveled with the queen through Panama, England, Italy, and the French Rivera. She was presented to Queen Victoria during Queen Emma's audience with the British monarch on September 9, 1865, and her overnight stay at Windsor Castle on November 27, 1865. 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". The extended royal trip continued onto the European continent. At Florence, her husband requested to return home and continue his clerical duties in Hawaii. Later at Turin, Kiliwehi was also permitted to accompany him back. 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 FinanceCharles Coffin Harris indicating they intended to take a "rather long round-about, and slow way toward home". Unknown to the Hawaiian government, the couple went to New Zealand to recruit Māori immigrants to settle in the Kingdom of Hawaii. This unauthorized excursion displeased the Hawaiian government and they were asked to return home. By the time the Kaʻauwais returned to Hawaii in 1867, Queen Emma had already returned as well. Back in Honolulu, her husband was shunned by King Kamehameha V because of his treatment of Queen Emma and the unauthorized visit to New Zealand. Domestic relations between Kiliwehi and her husband worsened. According to Kamehameha V, in one incident, Kaʻauwai placed a gun to her head and offered to shoot her. After this abuse, she left her husband and went to live at Haleʻākala, with High Chiefess Bernice Pauahi Bishop. Kiliwehi filed for divorce on April 22, 1872; the case went to trial on September 12 and she was granted a temporary decree which was made absolute on June 18, 1873. She was awarded ten dollars a month in alimony and Kaʻauwai was asked to cover the costs of the divorce suit. 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.
Death
Kiliwehi developed pulmonary tuberculosis, a serious disease among the Native Hawaiians which her husband also had. On October 12, 1873, she was sent from her home at Wailuku via Kahului to the Queen's Hospital in Honolulu for further treatment. Her friend Queen Emma wrote, "Poor Kiliwehi is at the Hospital and bleeding dreadfully at her lungs." Her condition worsened and she was moved from her hospital room to Haleʻākala, the home of Bernice Pauahi Bishop. Kiliwehi eventually died, on November 3, 1873, at Haleʻākala, Honolulu. She was 33 years old at the time of her death. Her funeral was held the following day at the St. Andrew's Pro-Cathedral.