The event is aimed at attracting investments into the manufacturing sector and showcasing success stories at a specially-created venue at the BKC business district in Central Mumbai.
Prime Ministers of Finland and Sweden and the deputy premier of Poland are also among the attendees.
After inaugurating the mega event, the Prime Minister took a tour of the pavilions, with his Swedish and Finnish counterparts and visiting ministers in tow.
Modi was scheduled to deliver a speech at an award event later in the evening.
"I can't speculate on the number of memoranda of understanding that will be signed, but this is a brilliant start. All our partners are very enthusiastic," Union Commerce Minister Nirmala Sitharaman told reporters later outside the main venue.
Over 2,500 international and 8,000 domestic companies are participating in the multi-sectoral industrial event, which is being attended by foreign government delegations from 68 countries and business teams from 72 nations.
"India never had this kind of participation from across the world. FDI has grown by 48 per cent in recent months and it will continue to grow in future," Amitabh Kant, Secretary of the Department of Industrial Policy and Promotion, which is organising the jamboree, told PTI outside the MMRDA Grounds.
Bhaskar Bhatt of Titan, the country's largest watch maker, said the visit of the Prime Minister to their stall was "very encouraging" and added that "this is a great country to invest as we have plenty of skilled manpower, technology and a large consuming class".
industry captains, including Ratan Tata, Cyrus Mistry, Mukesh Ambani, Ajay Piramal, Kumar Mangalam Birla, Anand Mahindra and Gautam Adani.
The host state, Maharashtra, is expecting to get investment proposals of over Rs 4 trillion from the event and announced one today with a USD 10 billion investment from an arm of the Vedanta group into a LCD panel manufacturing facility.
As many as 17 states, mostly BJP-ruled ones and the Congress-ruled Karnataka, are participating in the expo and there will be 52 seminars.
There will also be state-centric sessions on Gujarat, Madhya Pradesh, Haryana, Odisha and Punjab.
Piramal Group Chairman Ajay Piramal said this 'one-of-a-kind' event will showcase India's talent to innovate and deliver high-quality investments in real estate, financial services, infrastructure and pharma.
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