Gordon Strachan's side have the opportunity to avenge the 3-2 defeat to the English at Wembley last year when the two British teams go head-to-head in Glasgow four days after the Scots play their UEFA Euro 2016 Group D qualifier against Republic of Ireland at the same venue.
It will also be the first meeting in Scotland for 15 years since two goals from Paul Scholes gave England the advantage in a UEFA Euro 2000 play-off first-leg tie in November 1999.
Scotland won the second leg 1-0 at Wembley, Don Hutchison's goal giving them their most recent win over England, but it was not enough to see them into the tournament.
The two nations share close footballing ties, with the 0-0 draw in November 1872 recorded as the first official match between two football associations.
The confirmed 2014 contest, coming 142 years after the first meeting, will be the 112th time England and Scotland have faced one another. The records remain close, England having won 46 to Scotland's 41 with 24 draws.
Their only other meeting in the last 25 years came during the group stage of Euro 96, hosted by England, with an Alan Shearer header and a stunning Paul Gascoigne effort coming either side of a David Seaman penalty save to give the eventual semi-finalists a 2-0 win on home soil.
With Hampden Park undergoing renovation work, the game at Celtic Park will be the first game between the two sides not played in the national stadium since 1904.
The game will be England's last senior fixture of 2014 and comes three days after a Euro 2016 qualifier away to Slovenia.
Scotland's qualification campaign gets under way on September 7 against new world champions Germany in Dortmund.