RCom said it is holding non-binding, but exclusive talks, with Aircel's majority owner Malaysia's Maxis Communications and another shareholder Sindya Securities and Investments.
It entered into a 90-day 'exclusivity period' for the deal that will exclude RCom's tower and optical fibre assets for which a separate sale process is ongoing, the company said in a statement.
RCom is India's fourth-biggest telecom operator with almost 110 million customers, while Aircel ranks fifth with 84 million subscribers.
For its towers and fiber-optic infrastructure assets, RCom had earlier this month said that it is in talks to sell them to private equity firms Tillman Global Holdings LLC and TPG Asia Inc by mid-January.
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The merged entity will be created through equity deal where RCom's shareholders are looking for three shares against each held by them.
The debt of RCom, which is estimated go down below Rs 10,000 crore after its mobile tower sale deal is closed, will be transferred to this new entity and the company will become free of debt, sources said.
"RCom has expressed interest in focusing on enterprise business while the new entity, whose brand and other details will be finalised later, will run mobile business created by using resources of RCom, Aircel and MTS," they said.
The new entity, which is in the works, will hold spectrum across all allocated bands -- 800 Mhz, 900 Mhz, 1800 Mhz, 2100 Mhz and 2300 MHz -- for 2G, 3G and 4G services.
"With merger of MTS and Aircel, Reliance Communications will become a formidable entity with approximately 200 million subscribers. Furthermore, with spectrum consolidation, it can plan its longer term business strategy better," Gartner Research Director Amresh Nandan said.
RCom said the idea of potential combination of business with Aircel is to mutually derive expected substantial benefits of in-country consolidation, including operating expenditure (opex) and capital expenditure (capex) synergies and revenue enhancement.
"The discussions are non-binding in nature. Any transaction will be subject to due diligence, definitive documentation and regulatory, shareholders' and other third-party approvals. Hence, there is no certainty that any transaction will result," the company said.
The potential combination will exclude RCom's towers and optical fibre infrastructure, for which RCom is proceeding with an asset sale, as announced on December 4, 2015.
The stock of Reliance Communications today closed at 85.70, up 2.39 per cent on BSE.