According to reports, McLoughlin and Rooney will appear together in a TV and billboard campaign this Christmas in a deal that follows her £1.5m agreement with Asda clothing range George for its Must Have range, which launched in September.
Rooney was dropped as the face of Asda just three months into a £3m deal in July, following poor performances in the World Cup for England.
It is understood that McLoughlin and Rooney had previously wished to be viewed as "separate acquisitions" in ads, but the deal with Coca-Cola will mark the first time the couple have appeared in a campaign together.
McLoughlin already has a £500,000 contract with LG Mobile, to advertise its touchpad slide mobile phone, and helped launch the company's LG Chocolate Pink phone range in Manchester on Friday.
She has garnered an estimated £6m in ad deals, making her one of the most successful England WAGs, along with Victoria Beckham, who launched the Intimately Beckham scent range, and Girls Aloud singer Cheryl Tweedy, wife of Ashley Cole, who helped launch Coke Zero in July.
McLoughlin also has a £1.5m ad deal with Nike to promote its Nike C womenswear range.
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