The Tynecastle Park side was one of the top seeds and will be joined by Inverness CT, Peterhead, Cove Rangers and Stirling Albion in their group.
Clubs involved in Europe don't participate until the knock-out stage in mid-August, with Aberdeen, Celtic, Hibs, St Johnstone, and Rangers all involved in continental action.
The cup competition is now sponsored and screened exclusively by Premier Sport.
SPFL new boys Kelty Hearts were drawn in Group B with Dundee United, Arbroath, East Fife, and Elgin City while Scottish Premiership play-off winners Dundee will meet Ross County, Forfar, Montrose, and Brora Rangers.
Relegated Hamilton face Ayr United, Falkirk, Albion Rovers, and Edinburgh City while Kilmarnock will play Morton, Clyde, Stranraer, and East Kilbride.
Livingston are in Group D with Raith Rovers, Alloa, Cowdenbeath, and Brechin City while St Mirren, Dunfermline, Stenhousemuir, Partick Thistle, and Dumbarton will battle it out in Group H.
Motherwell are in Group F along with Queen of the South, Airdrie, Annan, and Queen's Park.
Group winners progress to the Premier Sports Cup’s knockout phase along with the three best runners-up.
Chairmen and directors across the country are hopeful fans will be allowed to attend Premier Sports Cup ties after a year when virtually every match was played behind closed doors due to the Covid-19 pandemic.
The first round of fixtures will be played on July 10/11 with the second on July 13/14. The third set of fixtures takes place on July 17/18 with the fourth following on July 20/21 and the fifth and final round of group games scheduled for July 24/25.
FULL PREMIER SPORTS CUP GROUP STAGE DRAW
Hearts, Inverness CT, Peterhead, Cove Rangers, Stirling Albion.
Dundee Utd, Arbroath, East Fife, Elgin City, Kelty Hearts.
Ross County, Dundee, Forfar, Montrose, Brora Rangers.
Livingston, Raith Rovers, Alloa, Cowdenbeath, Brechin City.
Hamilton, Ayr Utd, Falkirk, Albion Rovers, Edinburgh City.
Motherwell, Queen of the South, Airdrie, Annan Athletic, Queen’s Park.
Kilmarnock, Morton, Clyde, Stranraer, East Kilbride.
St Mirren, Dunfermline, Stenhousemuir, Partick Thistle, Dumbarton.