The machine stands about five-storeys tall and contains 42 cars, of various models, including the Ford Explorer SUV and Mustang.
Alibaba said users of Tmall, Alibaba's flagship online shopping platform, with good credit scores can buy a car from the machine, without any human help, in under 10 minutes.
They simply select a model on Alibaba's Taobao mobile app, have their face scanned by the app, and when they arrive at the machine, it will verify their identities before the vehicle is delivered.
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The vending machine will be open to the public from Monday to April 23. Buyers will be given a 3-day test drive before they have to commit to any purchase. Similar machines are being planned in Beijing and Hangzhou.
"Sign up is completely mobile on the Tmall or Taobao mobile APP," said Gu Wanguo, general manager of vehicles at Tmall Auto.
"Once a Ford vehicle is chosen, consumers snap a selfie to ensure they are only person who can take the car, put down a deposit electronically, and schedule a pickup time, all from within the app," he added. At Guangzhou's machine, buyers can also take out one other car if they are not satisfied with their selections.
Ford and Alibaba signed a three-year collaboration partnership last December, allowing the US car maker various new retail opportunities, from pre-sales, test drives and leasing options, through Tmall.
The e-commerce giant is no stranger to selling cars online and via mobile apps. In 2016, Maserati sold 100 cars in 18 seconds during a flash sale on Tmall.
Online car-buying has been gaining traction in recent years, with electric carmaker Tesla pioneering direct sales straight from the internet.
Alibaba owns South China Morning Post.