Bolton, 28, has a wealth of experience behind her at both state and national level and has previously captained her native Western Fury in the Women’s National Cricket League.
Commenting on the announcement, His Excellency General the Honourable Sir Peter Cosgrove AK MC (Retd) said: “Nicole is a wonder from the west. With great talent, skill and determination, she will lead our up-and-coming Aussie women cricketers against the formidable English team.
"No doubt the English will be readying themselves for a fierce challenge.”
The Governor-General’s XI will be selected by Cricket Australia and will be announced in the lead up to the match. Continuing the tradition established in the first two Governor-General’s XI fixtures, a representative from Cricket ADF will be included in the squad.
CA Chief Executive Officer James Sutherland said the Governor-General's XI provides a great opportunity to highlight the increased depth and growth of women’s cricket in Australia.
“Cricket is continuing to grow rapidly as a sport of choice for girls and women in Australia. Our female participation numbers are at record levels and are up 25% over the last 12 months. In schools, clubs and across the community, there are more and more opportunities to play our sport,” said Sutherland.
"Whilst a relatively new fixture in the Australian cricket calendar, the Governor-General's XI is an important one for players selected and our visiting teams. To that end, it is relevant to acknowledge the Governor-General’s outstanding initiative in inaugurating the match two summers ago.”
One of the most consistent opening batters in world cricket, Bolton said it was a privilege to be named captain of the Governor-General’s XI.
“It’s a real honour to be named captain of the Governor-General’s XI against what will be a challenging England side fresh off a World Cup win,” said Bolton.
“I’m excited to see the make-up of our squad, there’s so many talented players across the country so I’m hoping we can put on a real spectacle for the Sydney crowd.”
Australia will finalise their preparations ahead of the series opener on 22 October with two 50-over practice matches against the Queensland Fire in Brisbane and a three-day day-night fixture against an ACT Invitational XI at Manuka Oval.
England will also be in action with two warm-up matches against a Cricket Australia XI in Brisbane and a three-day day-night fixture against also against a Cricket Australia XI at Blacktown International Sportspark.
Commonwealth Bank Women’s Ashes tour matches
16 October – Australia v Queensland Fire, Allan Border Field, Brisbane
16 October – England v Cricket Australia XI, Brisbane (tbc)
18 October – Australia v Queensland Fire, Allan Border Field, Brisbane
18 October – England v Cricket Australia XI, Brisbane (tbc)
Three-day day-night matches
3-5 November, Australia v ACT Invitational XI, Manuka Oval, Canberra
3-5 November, England v Cricket Australia XI, Blacktown International Sportspark, Blacktown
Commonwealth Bank Women’s Ashes matches
22 October – Allan Border Field, Brisbane
26 October – Coffs International Stadium, Coffs Harbour
29 October – Coffs International Stadium, Coffs Harbour
9-12 November – North Sydney Oval, North Sydney
17 November – North Sydney Oval, North Sydney
19 November – Manuka Oval, Canberra
21 November – Manuka Oval, Canberra