In the 1861 census Ann is listed as the wife, but she was actually unmarried. She was living with her widowed mother Priscilla, and her nephew Noah Knowles at that time.
Married Edgar Littley, the baker from Ottery St Mary in 1864 (aged 37) and had 2 sons, Edwin and Frederick.
In the 1871 census, Ann Littley's niece Augusta Evans had joined the family. Augusta's mother was Ann's sister Mary Evans, nee Stone, who had died in childbirth. Mary left behind 3 daughters, all under 4 years of age. Her husband James Evans seems not to have been able to cope and by 1871, he had parcelled his daughters out to the relatives. He may also have died as he disappears from all the records around this time.
Sources
1841 census - "England and Wales Census, 1841," database with images, FamilySearch (https://familysearch.org/ark:/61903/1:1:MQTN-YBV : 13 December 2017), Ann Stone in household of Precilla Stone, Aylesbeare, Devon, England; from "1841 England, Scotland and Wales census," database and images, findmypast (http://www.findmypast.com : n.d.); citing PRO HO 107, The National Archives, Kew, Surrey.
1851 census - "England and Wales Census, 1851," database with images, FamilySearch (https://familysearch.org/ark:/61903/1:1:SGNT-53N : 9 November 2017), Ann Stone in household of Precilla Stone, Aylesbeare, Devon, England; citing Aylesbeare, Devon, England, p. 31, from "1851 England, Scotland and Wales census," database and images, findmypast (http://www.findmypast.com : n.d.); citing PRO HO 107, The National Archives of the UK, Kew, Surrey.
1861 census - "England and Wales Census, 1861," database with images, FamilySearch (https://familysearch.org/ark:/61903/1:1:M7P1-SLJ : 11 December 2017), Ann Stone in household of Prescilla Stone, Aylesbeare, Devonshire, England; from "1861 England, Scotland and Wales census," database and images, findmypast (http://www.findmypast.com : n.d.); citing PRO RG 9, The National Archives, Kew, Surrey.
1871 census - "England and Wales Census, 1871", database with images, FamilySearch (https://familysearch.org/ark:/61903/1:1:V5T9-ZFG : 10 December 2017), Ann Littley in entry for Edgar Littley, 1871.
1881 census - "England and Wales Census, 1881," database with images, FamilySearch (https://familysearch.org/ark:/61903/1:1:Q276-GQKZ : 18 August 2016), Ann Littley in household of Edgar Littley, Ottery St Mary, Devon, England; from "1881 England, Scotland and Wales census," database and images, findmypast (http://www.findmypast.com : n.d.); citing p. 25, Piece/Folio 2134/69, The National Archives, Kew, Surrey; FHL microfilm 101,774,762.
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DNA Connections
It may be possible to confirm family relationships with Ann by comparing test results with other carriers of her mitochondrial DNA.
However, there are no known mtDNA test-takers in her direct maternal line.
It is likely that these autosomal DNA test-takers will share some percentage of DNA with Ann: