After graduating from Wellesley College with a degree in the History of Art, she began her career as a painter, and became involved in photography in 1970. Mostly self-taught in photography she makes ephemeral constructions to photograph and experiments with the endless possibilities of light. She has had more than one hundred one-person exhibitions in the United States and abroad, and her work is represented in major private, corporate, and museum collections, including the Art Institute of Chicago, the Museum of Modern Art in New York, the Museum of Fine Arts, Boston, and the International Museum of Photography at George Eastman House in Rochester, New York. Portfolios of her work have been published in Art News, American Photographer, Camera, Camera Arts, The Sciences and numerous other magazines in the United States, Europe, and Japan. There have been three monographs of Parker's work: Signs of Life (Godine, 1978), Under the Looking Glass (New York Graphic Society, 1983), and Weighing The Planets (New York Graphic Society, 1987). She has lectured and conducted workshops extensively both in this country and abroad. In 1996 she received a Wellesley College Alumnae Achievement Award. Residencies include Dartmouth College in 1988, The MacDowell Colony in 1993 and The Isabella Stewart Gardner Museum in 1997. In 1998 she did the title sequence for the PBS Television documentary Africans in America. In 2002-3 Parker Photographed in Anhui Province, China for The Peabody Essex Museum.

Olivia Parker makes black and white and color photographs in many formats from 35mm to Polaroid 20x24. Also, since 1993 she has been using her photographs as source material for digital images. In 2000 she began to use digital cameras for straight work as well as composite. Presently she is using Canon D60, 1D and 1Ds cameras. From 1993-2002 the composites became Nash Editions digital prints. Although she has been making smaller prints in her own studio since 1993 it was only in 2003 that Parker started making her own large format digital prints both straight and composite with an Epson 7600.

At present she is working on two groups of studio images as well as the China project: A History of The Real and Object/Space. A History of The Real involves toys, games and teaching aids, as well as the stuff of ordinary still life intersecting with fragments of the history of science. In Object/Space objects become still life but they move out of traditional intimate space into broader areas of photographic space.