Financial terms of the deal were not disclosed.
In June, Walmart said it was expanding transportation pilots with the manufacturers of electric, hydrogen and natural gas-powered vehicles, including Cummins Inc and Daimler Truck's Freightliner.
The retailer in January said it had reserved 5,000 electric delivery vans with General Motors' commercial EV business, BrightDrop.
A large number of companies have been pushing into the growing commercial EV space as governments around the world are pressing companies to slash CO2 emissions.
Companies including FedEx Corp, Amazon.com Inc and United Parcel Service Inc have pledged to shift their large delivery fleets to EVs.
The deal announced on Tuesday also includes Canoo's fully electric Lifestyle Delivery Vehicle (LDV). The EV startup anticipates starting production of the LDVs beginning in the fourth quarter of 2022, according to the statement.
Canoo chief executive officer Tony Aquila said the firm expects to build 14,000 to 17,000 vehicles in 2023.
"By continuing to expand our last mile delivery fleet in a sustainable way, we're able to provide customers and Walmart+ members with even more access to same-day deliveries while keeping costs low," said David Guggina, senior vice president of innovation and automation at Walmart US.