The former England, Arsenal and Boston Breakers right-back ended her playing career at the end of last season.
And Scott, 33, clocked up 140 caps for the Lionesses during her 16-year career, while clinching five Women's Premier League titles, seven women's FA Cups and the Women's Champions League.
She was part of the BBC's punditry team at the World Cup in Russia earlier this summer and has been well received for her work.
And according to The Times, Scott will be part of Sky's punditry team for Super Sunday alongside Graeme Souness and Jamie Carragher as West Ham welcome Liverpool to the London Stadium 1.30pm.
Arsenal then take on Manchester City at 4pm at the Emirates to conclude the opening weekend of Premier League fixtures.
Scott told The Times: "I am pinching myself.
"I have been working towards this for the past two years."
Scott was also a Fifa ambassador during this summer's tournament and was pictured sitting down with Russian president Vladimir Putin and other football ambassadors in Moscow.
Kelly Cates is set to host Sky Sports' coverage of tonight's Premier League clash between Manchester United and Leicester City.
And Juventus star Eni Aluko also made a big breakthrough on ITV's World Cup coverage this summer, while former France full-back Patrice Evra was criticised for applauding her analysis in an apparently patronising manner.
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