Jones, 17, has replaced Maya Joint in the squad after the Australian No.1 was forced out as she continues her recovery from a back injury.
Captained by retired great Sam Stosur, the Australian team comprises Jones, Talia Gibson, Kimberly Birrell, Storm Hunter and Ellen Perez.
The group have been preparing in Melbourne, with the two-day qualifying tie at John Cain Arena starting on Friday.
Former world No.1 junior Jones was a training partner with the squad a year ago and said she was comfortable wearing the green and gold.
If she gains an opportunity, Jones will be one of the youngest debutants in the history of the competition which, formerly known as the Federation Cup, dates back to 1963.
"It's great to be back - last time I was orange girl and that was great fun but to actually be in the team this year is really exciting for me," said the world No.134.
"To compete and play for Australia is really a privilege."
Former world No.1 doubles star Hunter was excited to play in front of local fans, with Melbourne hosting a BJK Cup tie for the first time in 15 years.
She said it was a blow to lose the in-form Joint, who is ranked 30, but backed her team to get the job done against Great Britain.
The visitors are missing their four best players with Emma Raducanu, Katie Boulter and Francesca Jones opting to focus on the European clay-court swing.
British No. 2 Sonay Kartal, is a recent casualty after she injured her back at the Indian Wells Open last month.
"It's unfortunate for Maya, being withdrawn last week but it's an amazing opportunity for Emerson," Hunter said.
"It's really nice for 'Emo' to make her debut. She's obviously been orange girl here before with the team so she knows how things roll but for her to make her debut is really special.
"For me it's really cool to be a part of that. She's super young and for her to be the next gen, along with Talia, is really exciting."
The teams will compete in a best-of-five-rubber format, consisting of four singles matches and one doubles match. The winner of the tie will advance to the eight-nation Finals, scheduled for September in China.
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