[citation needed] After they married, her husband became a member of the U.S. House of Representatives in 1879, serving until 1881 when he was appointed the United States Minister to France by President James A. Garfield in 1881.

During her husband's term as Vice President of the United States under President Benjamin Harrison, she was Second Lady of the United States from 1889 to 1893 and often handled entertaining duties for the administration due to First Lady Caroline Harrison's illness and ultimate death.

In 1873, Anna was married to Levi Parsons Morton (1824–1920), just two years after the death of his first wife, Lucy Young Kimball, in 1871.

A son, Lewis died at the age of four months in London, and daughters Lena and Alice predeceased their mother.

In January 1905, The New York Times revealed that the Mortons were the givers, including funds for the purchase of an organ in memory of their daughter Lena who died in Paris the June previous.