Hibernian continue their defence of the CIS Insurance Cup at home to Motherwell in the third round of the tournament.
Celtic will travel to First Division Dundee, while Third Division leaders East Fife host Rangers.
Inverness entertain Gretna and fellow SPL sides Falkirk and Dundee United must do battle.
Hearts are at home to Dunfermline, First Division pace-setters Hamilton host Kilmarnock and Aberdeen face a trip to Partick Thistle.
Ties will be played on 25 September or 26 September and BBC Scotland will provide live television coverage of the Dundee v Celtic tie.
East Fife were the first team to win the Scottish League Cup three times after their triumphs in 1947, 49 and 53.
Premier League leaders Rangers won it in 1946 and 48 and have lifted the trophy on 22 other ocassions, while the Fifers' fortunes have waned since the 1950s.
However, the Methil side have already claimed a top flight scalp, knocking St Mirren out in the previous round with a 1-0 win at Love Street.
And vice-chairman Sid Collumbine told BBC Sport: "This tie is not about the money. It's about honour.
"I'm so proud of the team for having got this far in the competition with a great victory over St Mirren."
CIS Insurance Cup - third round draw:
Inverness CT v Gretna
East Fife v Rangers
Falkirk v Dundee United
Dundee v Celtic
Hearts v Dunfermline Athletic
Hamilton Accies v Kilmarnock
Hibernian v Motherwell
Partick Thistle v Aberdeen
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