The matches will be played on the opening weekend of the new season and will feature a number of The Football League's founder members, as well as other pairings of historical significance.
In the Championship, four of The League's founder members will go head-to-head with Derby County, League champions in 1972 and 1975 hosting Blackburn Rovers, champions of England in 1912, 1914 and 1995.
Lancashire rivals Burnley and Bolton Wanderers will face each other at Turf Moor, one of only three grounds used in the 1888/89 season that is still in use today. The two clubs have met each other on 114 occasions since league football began.
Another of the original grounds, Deepdale, will host the meeting of founder members Preston North End and Wolverhampton Wanderers in League 1. Since hosting its first league match on the opening day of the 1888/89 season, Deepdale has staged 2,342 Football League matches, more than any other stadium. Also in League 1, the world's oldest Football League club, Notts County will be the visitors at the world's oldest professional football ground - Bramall Lane, home of Sheffield United.
In League 2, Accrington Stanley will visit The Football League's newest ground and newest member - Rodney Parade the home of the re-formed Newport County. While Hartlepool United will meet Rochdale in the 137th encounter between the two clubs, the most played Football League match between current League members.
In announcing the 125th Anniversary fixtures, Football League Chairman Greg Clarke said:
"For 125 years, Football League clubs have delivered the greatest show in town, week after week. In the process, attracting a total audience of more than 2.2 billion people and building indelible relationships with their local communities.
"Our clubs and their supporters are the heartbeat of the domestic game, giving English league football a breadth and popularity that is unrivalled anywhere in the world.
"We look forward to celebrating 125 years of incredible matches, unforgettable moments and gloves-off footballing rivalry."