Celtic beat Glasgow rivals Rangers in the final last season, with Kyogo Furuhashi's double sealing a 2-1 win at Hampden Park.
Match preview
Celtic returned to form on the road by beating Aberdeen 3-1 in their first away match of the season at the weekend.
With the title already secured, Celtic took their foot off the gas a little at the end of last season and lost their final two matches away from home, conceding seven.
The win at Aberdeen sees them top the Scottish Premiership after two matches, with only them and St Mirren still maintaining a 100% record.
Brendan Rodgers and his side will hope to navigate this tie and the upcoming league fixture with St Johnstone without much fuss, before the first Old Firm clash of the season on September 3.
Kilmarnock are a side that Celtic comfortably brushed aside on many occasions last season too, winning all four meetings by an aggregate score of 13-1.
Just three wins over Celtic at Rugby Park since 2001 illustrates the tall order facing Killie ahead of this cup tie.
Derek McInnes's side have already caused a major shock in Scottish football this season, though, beating Rangers on the opening day.
Bradley Lyons's goal midway through the second half sealed a 1-0 win here at Rugby Park, and it remains the only goal seen in their league campaign so far.
Another successful shutout in a 0-0 draw at Hearts over the weekend means the Killie goal has yet to be breached.
Kilmarnock edged past Raith Rovers to take top spot in their League Cup group, but have now been handed the toughest possible draw.
Kilmarnock Scottish League Cup form:
W
W
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W
Kilmarnock form (all competitions):
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W
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W
W
D
Celtic form (all competitions):
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Team News
Celtic are set to be without Reo Hatate for this encounter after he went off not long after coming on as a half-time substitute against Aberdeen.
Hatate would have likely been one of the players brought in as rotation, so Rodgers may need to go stronger in midfield than he would have preferred.
Gustaf Lagerbielke has arrived from Elfsborg this week and could be in line for a debut in defence.
Yuki Kobayashi and Hyeongyu Oh are also set to miss out though, having not featured for Celtic in the league yet this season.
For Kilmarnock, they should have a full-strength side available to them once again here to face the holders.
Manager McInnes has gone with his first-choice side throughout much of their League Cup campaign so far and could remain unchanged from last weekend.
Kilmarnock possible starting lineup:
Dennis; Mayo, Deas, Findlay; Armstrong, Lyons, Watson, Magennis, Ndaba; Kennedy, Watkins
Celtic possible starting lineup:
Hart; Ralston, Lagerbielke, Nawrocki, Taylor; O'Riley, Iwata, Turnbull; Haksabanovic, Kyogo, Maeda
We say: Kilmarnock 0-3 Celtic
Even if Rodgers rings the changes, Celtic still should have enough to see off Kilmarnock here.