Anna Catherine Wiley was born in Coal Creek, Tennessee, but was raised in Knoxville. She enrolled at the University of Tennessee in 1895 and later continued her education at the Art Students League in New York with Frank Vincent Dumond and Robert Reid among her instructors. She also briefly studied at The New York School of Art before she returned to Knoxville and accepted a teaching position at the University of Tennessee, which she held for fourteen years. During the summer months she studied Impressionism in the Northeast with American Impressionists Robert Reid, Jonas Lie, and Martha Walter. In Knoxville Wiley was a member of the Nicholson Art League, a group of leading Knoxville artists during the first quarter of the twentieth century, and she was active in organizing exhibitions for its members. Throughout her career Wiley received instruction from prominent Knoxville artist, and founder of the Nicholson Art League, Lloyd Branson.
Around the turn of the century, Impressionism was extremely popular among artists in the South because it effectively captured the emotional connection felt by many to the land. Many of Wiley’s paintings feature upper class subjects—women and children relaxing on a lawn or similar scenes of quiet situations. Like other American Impressionists, Wiley did not fully dissolve the subject into light and movement, but rather used rapid brushstrokes for emphasis and emotional impact. However, as time went on her style did undergo changes and became more abstract and focused on color patches instead of figures.
While Wiley won regional awards for her artwork, she never reached the national acclaim she desired. She applied for admission into the National Academy of Design several times between 1915 and 1925 only to be rejected repeatedly. It has been suggested that this rejection was a factor that led to her emotional breakdown and mental collapse in 1926. She was institutionalized and though she lived until 1958, she never painted again.