British No 1 Dan Evans and Neal Skupski also feature in Leon Smith's squad, while a fifth player will be confirmed in the coming weeks.
Andy Murray's inclusion comes a day after his remarkable victory over Stan Wawrinka in the ATP Antwerp final.
Playing in just his seventh singles tournament since returning from hip surgery, Murray battled from a set down to beat his fellow three-time Grand Slam champion.
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"It’s been absolutely fantastic to see Andy back competing again including his incredible win in Antwerp yesterday," Smith said.
Meanwhile, Evans gets the nod after emerging as Britain's highest-ranked player, having broken into the top 50.
Smith added: "Dan is playing some of the best tennis of his career and firmly deserves his place back inside the world’s Top 50.
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“Jamie and Neal have been gaining much momentum as a team with impressive semi-final runs at Cincinnati, US Open, Beijing and Shanghai. We are in a good position with improved strength and depth in our team and will be naming the fifth player in the next couple of weeks.
"We are looking forward to bringing our best tennis to the group phase and as always, we are excited to play for our many home fans and all those travelling out to Madrid.”
The finals take place in Madrid from November 18-24.
Great Britain are in Group E along with the Netherlands and Kazakhstan, and face them on Wednesday 20 and Thursday 21 respectively.
The quarter-finals take place on Friday 22, with the semi-finals on Saturday 23 and the final on Sunday 24.