The last time the two teams faced each other was in this round of the competition 11 years ago, with the Dons winning 3-2 on home soil.
Match preview
After being eliminated in the League Cup group stages in each of the previous five seasons, Raith Rovers finally progressed to the second round, finishing top of Group D with nine points from their four matches.
Despite losing 6-5 on penalties to Livingston, a shootout win against Alloa Athletic as well as victories in 90 minutes against Cowdenbeath and Brechin City, ensured John McGlynn's men finished top of their group and as one of six teams who remain unbeaten in the competition.
Since the group stages came to a conclusion, Raith have not had the best of starts in the league. In their opening fixture, they let a four-goal lead slip in the final 25 minutes against Hamilton Academical, drawing a remarkable clash 4-4 on home soil, before narrowly losing 1-0 against Inverness Caledonian Thistle last weekend, with Roddy MacGregor scoring an 80th-minute winner.
McGlynn, who will be slightly concerned that his side have struggled to see out games in the latter stages, now faces a much tougher task against Premiership opposition, though they were able to hold their own against Livingston three weeks ago.
Progression to the next round is unlikely for the Championship side, but they are sure to put up a fight in front of their own fans.
Aberdeen followed up their 2-0 Premiership victory over Dundee United on the opening day with a 2-1 win away at Livingston last weekend.
Former Dons forward Bruce Anderson gave the Lions the lead in the 35th minute, however second-half strikes from Teddy Jenks and Jack MacKenzie turned the game on its head to seal all three points for the visitors.
Since then, Aberdeen progressed into the Europa Conference League playoff round when they beat Icelandic side Breidablik 2-1 at Pittodrie in the second leg on Thursday, winning 5-3 on aggregate.
The Dons have not competed in the group stages of a major European competition since the 2007-08 campaign when they were knocked out of the UEFA Cup by German giants Bayern Munich in the round of 32.
A playoff tie against Azerbaijani side Qarabag is just round the corner, but Stephen Glass must first turn his attention to Sunday's clash with Raith, a side they have failed to beat in both of their last two visits.
The Dons have, however, looked strong in the early stages of this campaign and they will be confident in defeating lower league opposition this weekend.
Raith Rovers Scottish League Cup form:
Raith Rovers form (all competitions):
Aberdeen form (all competitions):
Team News
Raith boss McGlynn is set to stick with a three-man defence of Kyle Benedictus, Tom Lang and former Scotland international Christophe Berra, with Reghan Tumilty and Liam Dick to operate as wing-backs.
Canadian attacker Dario Zanatta, who has contributed to three goals in his last five games, is expected to start in the number 10 role in behind new recruit Matej Poplatnik.
As for Aberdeen, they remain without centre-back Michael Devlin, who is suffering with an ankle injury.
With one eye on their playoff match in Europe, Glass may decide to rest some players, which could see the likes of Niall McGinn, Jack Gurr and youngster Dean Campbell handed starts this weekend.
New arrival Christian Ramirez, who has scored four goals in six competitive matches so far this season, could also be given a break with Jay Emmanuel-Thomas the most likely candidate to replace him up front.
Raith Rovers possible starting lineup:
MacDonald; Lang, Berra, Benedictus; Tumilty, Connolly, Matthews, Tait, Dick; Zanatta; Poplatnik
Aberdeen possible starting lineup:
Lewis; Gurr, Gallagher, Considine, MacKenzie; Ojo, Jenks, McGeouch, Campbell, McGinn; Emmanuel-Thomas
We say: Raith Rovers 0-3 Aberdeen
Despite keeping clean sheets in all four of their group stage matches, Raith may struggle to keep Aberdeen's attackers at bay this weekend.
The visitors have scored 14 goals in their six competitive fixtures so far this season, and we can see them adding to that total on Sunday, securing a comfortable victory at Stark's Park.