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Ocado shares jumped more than 40% following the announcement, while Morrisons was up by 1% in the FTSE 100 Index.
Ocado chief executive Tim Steiner said the agreement with Morrisons would have no impact on its existing arrangements.
The launch will see the retailer use Ocado's recently opened distribution centre in Warwickshire for deliveries through a Morrisons-liveried fleet.
The 25-year deal involves Morrisons paying up to £170 million to Ocado to acquire the site and equipment.
Supermarket Morrisons is to start its online groceries business by the end of this year after unveiling a tie-up with delivery firm Ocado.
Ocado is closely linked with Waitrose, exclusively delivering the supermarket's products - as well as its own and those of branded ranges - to its customers and the move is likely to spark a backlash.
Mark Price, managing director of Waitrose, recently told The Sunday Telegraph its lawyers would seek to examine any tie-up between the other two companies.