Walton was born in Newport, Arkansas. She was raised along with her 3 brothers in Bentonville, Arkansas and graduated from Bentonville HS in 1966. She graduated from Trinity University in San Antonio, Texas, with a B.A. in economics.

Walton married a prominent Louisiana investment banker in 1974 at age 24, but they were divorced 2½ years later. According to Forbes, she married “the contractor who built her swimming pool” soon after, “but they, too, divorced quickly”.

In her early career, Walton was an equity analyst and money manager for First Commerce Corporation and headed investment activities at Arvest Bank Group. She was also a broker for EF Hutton. In 1988, Walton founded Llama Company, an investment bank, where she was president, chairwoman and CEO.

Walton has been involved in multiple automobile accidents, one of them fatal. She lost control of a rented Jeep during a 1983 Thanksgiving family reunion near Acapulco and plunged into a ravine, shattering her leg. She was airlifted out of Mexico and underwent more than two dozen surgeries; she suffers lingering pain from her injuries. In April 1989, she struck and killed 50 year-old Oleta Hardin, who had stepped onto a road in Fayetteville, Arkansas. Witnesses stated that Walton was speeding at the time, but no charges were filed. In 1998, she hit a gas meter while driving under the influence of alcohol. She paid a $925 fine.

In his 1992 autobiography Made in America, Sam Walton remarked that Alice was “the most like me—a maverick—but even more volatile than I am.”

Walton was the first person to chair the Northwest Arkansas Council and played a major role in the development of the Northwest Arkansas Regional Airport, which opened in 1998. At the time, the business and civic leaders of Northwest Arkansas Council found a need for the $109 million regional airport in their corner of the state. Walton provided $15 million in initial funding for construction. Her company, Llama Company, underwrote a $79.5 million bond. The Northwest Arkansas Regional Airport Authority recognized Walton’s contributions to the creation of the airport and named the terminal the Alice L. Walton Terminal Building. She was inducted into the Arkansas Aviation Hall of Fame in 2001.

In the late 1990s, Llama Co. closed and, in 1998, Walton moved to a ranch in Millsap, Texas, named Walton’s Rocking W Ranch. An avid horse-lover, she was known for having an eye for determining which 2-month-olds would grow to be champion cutters. Walton listed the farm for sale in 2015 and moved to Fort Worth, Texas, citing the need to focus on the Crystal Bridges Museum of American Art, the Bentonville, Arkansas, art museum she founded that opened in 2011.

In December 2004, Walton purchased art sold from the collection of Daniel Fraad and Rita Fraad at Sotheby’s, in New York.

In 2005, Walton purchased Asher Brown Durand’s celebrated painting, Kindred Spirits, in a sealed-bid auction for a purported US$35 million. The 1849 painting, a tribute to Hudson River School painter Thomas Cole, had been given to the New York Public Library in 1904 by Julia Bryant, the daughter of Romantic poet and New York newspaper publisher William Cullen Bryant, who is depicted in the painting with Cole. She has also purchased works by American painters Winslow Homer and Edward Hopper, as well as a notable portrait of George Washington by Charles Willson Peale, in preparation for the opening of Crystal Bridges. In 2009, Walton acquired Norman Rockwell’s “Rosie the Riveter” for $4.9 million.

In a 2011 interview, she spoke about acquiring great works by other artists. She described Marsden Hartley as “one of my favorite artists-he was a very complex guy, somewhat tormented, but a very spiritual person, and love the emotion and the feel and the spirituality of his work”. She went on to say “and Andrew Wyeth-the mystery and loneliness that is expressed. How do you paint loneliness?”

Alice Walton was the 20th-largest individual contributor to 527 committees in the U.S. presidential election 2004, donating US$2.6 million to the conservative Progress for America group. As of January 2012, Walton had contributed $200,000 to Restore Our Future, the super PAC associated with Mitt Romney’s presidential campaign. Despite hailing from a largely Republican family, Alice donated $353,400 to the Hillary Victory Fund, a joint fundraising committee supporting Clinton and other Democrats, in 2016.