The visitors enter the competition at this stage, while their hosts progressed through their first-round group to reach the final 16.
Match preview
Motherwell head into the Scottish League Cup second round on Sunday with their sights set on reaching the quarter-finals, having fallen at this stage at the hands of St Mirren.
Their latest campaign began in the first-round group stage, and the Well progressed in first place, earning nine points from their four outings having beaten Edinburgh City and Clyde 3-0 and 3-1 respectively while playing out draws with Montrose and Partick Thistle, having earned a bonus point by beating the former in the subsequent penalty shootout.
Since that successful group run, Stuart Kettlewell's side have kicked off their latest Scottish Premiership campaign on the back of a ninth-placed finish last time around, firstly hosting Ross County and playing out a goalless draw in their curtain-raiser at the beginning of August.
A tough trip to title-chasing Rangers then followed on Saturday, and the Well fell just short, eventually succumbing to a 2-1 defeat at Ibrox having drawn level through a Robin Propper own goal in the opening 20 minutes, only for Vaclav Cerny to restore the hosts' lead shortly after.
With positives to take from that display in the capital, Motherwell will now turn their focus back to the League Cup with the aim of progressing further with another victory at Fir Park.
That will be no easy task, though, as the visitors arrive following an impressive victory in midweek on the continent.
Thanks to a fourth-placed Scottish Premiership finish last time around, Kilmarnock earned a bye through the League Cup group stage and a place in Europa League qualifying, and after a 2-1 aggregate defeat to Cercle Brugge, they dropped into qualifying for the Europa Conference League in the third round, meeting Norwegian outfit Tromso with a playoff place on the line.
Following a 2-2 draw in the home leg of that tie, Killie hosted St Johnstone on Sunday and suffered a 3-0 beating, leaving them without a point from two top-flight outings having conceded seven goals while failing to score.
Aiming to put that disappointment behind them, Derek McInnes's side travelled north for the reverse fixture of their qualifying tie on Thursday and progressed to the playoff round with a first competitive victory on the continent since 2001, having stood strong throughout the contest after Joe Wright netted the only goal on the night in the 11th minute.
With spirits bound to be high after that triumph, in spite of their poor start in Scotland's top flight, Kilmarnock will now set out to make it back-to-back wins on Sunday to punch their ticket to the League Cup quarter-finals.
Motherwell Scottish League Cup form:
W
W
W
L
Motherwell form (all competitions):
W
W
W
L
D
L
Kilmarnock form (all competitions):
D
L
L
D
L
W
Team News
Stuart Kettlewell should field a similar Motherwell starting XI to the one that featured in last week's trip to Rangers, although he will be unable to call on new striker Apostolos Stamatelopoulos, who sustained an injury in the first half of that contest.
In his absence, and following the summer departure of last season's top scorer Theo Bair, Zach Robinson should come in to lead the line from the start, while Moses Ebiye could come in to offer further attacking support, with returning striker Tony Watt also competing to start after arriving on loan from Dundee United.
The Well continue to deal with several other injury issues, as John Koutroumbis, Ross Callachan, Filip Stuparevic, Callum Slattery and Sam Nicholson are all set to remain confined to the treatment room.
Kilmarnock should also head into Sunday's contest with a similar starting XI from their midweek Europa Conference League qualifying win, with attacker Marley Watkins set to remain out of action.
In his absence, Bobby Wales could again lead the line alongside key man Kyle Vassell, who netted 11 goals last season, while Matty Kennedy and Danny Armstrong will offer further attacking threat from the wings.
Bradley Lyons and Liam Donnelly are mainstays in the engine room, while Robbie Deas will hope to earn a spot in the defence after Lewis Mayo, Joe Wright, Stuart Findlay and Oliver Bainbridge lined up in a back four on Tuesday.
Motherwell possible starting lineup:
Oxborough; McGinn, Gordon, Casey; O'Donnell, Halliday, Zdravkovski, Seddon; Ebiye, Robinson, Wilson
Kilmarnock possible starting lineup:
McCrorie; Mayo, Findlay, Deas; Armstrong, Lyons, Donnelly, Murray, Kennedy; Vassell, Wales