It comes as supermarkets throw away millions of pounds in a digital gold rush after an internet grocery surge triggered by Covid.
Meanwhile, Dame Sharon White, boss of parent company John Lewis Partnership, is looking to make the company a digital champion with a series of sweeping reforms.
Amazon bought 16pc of Deliveroo earlier this year in a contentious deal that has been tightly controlled by competitive watchdogs.
The $ 1.7 trillion (£ 1.3 trillion) American titan is already fighting to expand its presence in British online food through its Fresh arm, which stocks Morrisons products.
Last month, it became the first player to offer free shipping to customers using the Amazon Prime subscription service in what was seen as a turning point for the industry, and it is believed to plan to roll out 30 of its “Go” stores without payment. Great Britain.
Amazon founder Jeff Bezos is rumored to have had talks to buy Waitrose in 2018, a claim vehemently rejected by John Lewis.
Richard Hyman, a retail analyst, said, “To learn from history, Amazon doesn’t do anything frivolously.
“Could I ever see Amazon and Waitrose go to bed?” Absolutely. ”
Dame Sharon took over John Lewis in February and vowed to turn around the ailing mutual, which was already struggling before Covid hit and was then hammered by the lockdown.
She has already closed eight department stores with 1,800 jobs at risk and describes a series of new measures to relaunch the brand, including transforming underused sites into social housing, opening garden centers and making it possible for customers to rent. furniture rather than buying it.
The Deliveroo deal will initially be offered in stores in Bracknell, Clifton, Surbiton, Cambridge and Notting Hill.
It comes a day before the end of a long-standing relationship between Waitrose and Ocado, which will begin stocking Marks & Spencer products from Tuesday. Waitrose continued to offer grocery delivery products directly through its own website.
Over 500 products will be available through Deliveroo, far less than the 4,000 sold through Ocado.
The trial is designed to complement Waitrose’s “Rapid” service, which has approximately 23,000 customers following a triple peak during the pandemic and delivers in two hours or less.
Waitrose executive director James Bailey said the lawsuit had “enormous potential”.
He added: “We have set a milestone for our future strategy with the growth of Waitrose.com and Waitrose Rapid, and this gives us another opportunity to give our customers a taste of what the future might look like. of the convenience store for us.
The company said the trial “underscored its ambition” to use new partnerships to get goods to customers. If successful, Waitrose will expand to more places.
Ajay Lakhani, vice president of new businesses at Deliveroo, said: “Deliveroo’s on-demand grocery services have proven to be vital for many people during this difficult time, allowing families to quickly get the items they want. need and need without having to leave home.
Online grocery shopping has exploded during the lockdown and the market is expected to grow by more than a third to £ 16.8 billion this year, according to market research firm Mintel.
This profound change surprised food industry executives, many of whom believed consumer behavior would never change after years of sluggish digital growth.
This has sparked a race for market share, with Tesco announcing earlier this week plans to hire an additional 16,000 employees thanks to surging online sales.
Mr Hyman said, “The pandemic has changed everything dramatically and introduced many more people to online shopping,” he said.
“In a very short period of time, we have seen five years of development concentrated in a few weeks.”