Jain, who left Walmart India in June last year, will report to Bharti Enterprises Vice Chairman and Managing Director Rajan Bharti Mittal, the company said in a statement.
Madan, who was CFO at Bharti Walmart, had left the cash and carry firm in the wake of investigations of corruption allegations by Walmart in 2012.
Commenting on the appointments, Mittal said: "Bharti is committed to building a world-class retail venture and we are delighted to have Raj and Pankaj on board. I am confident that their rich experience and insights into the retail business will add immense value to company's growth plans."
In October last year, Bharti Enterprises and Walmart had announced they were parting ways to operate retail stores independently in India, ending speculation over the future of their six-year-old partnership.
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Subsequently, the US retail major would buy out its Indian partner in their 50:50 cash-and-carry joint venture Bharti Walmart, which runs 20 wholesale stores under the Best Price Modern Wholesale brand in India, for an undisclosed sum.
At the time of the break up, Jain was roped in as an advisor by the Bharti Group. Earlier, he was the Asia Pacific Region Head, Marketing and Supply Chain at Whirlpool Corporation in Shanghai and had also served as Managing Director & CEO of Whirlpool of India Ltd.