Burnley, Leicester and Birmingham are in a position to upset Premier League opposition, while the showdown between the Gunners and the Blues is too close to call
While the clash between London giants and the teams sitting in first and second position on the EPL table in Arsenal and Chelsea is the clear stand-out fixture of the night - that game looks a difficult proposition from a betting point of view.
That is because there is uncertainty over how strong a side both clubs will field, given the League Cup remains a low priority behind the pursuit of the EPL title and their Champions League campaigns.
Outspoken Chelsea manager Jose Mourinho has already threatened to field an under strength side - angered by the fact the match has been scheduled just 48 hours after Sunday's EPL blockbuster against Manchester City.
And Arsenal manager Arsene Wenger regularly uses the competition to play his youngsters, with the Gunners not having won the competition since 1993 although they were runners-up in 2007 and 2011.
Chelsea - League Cup winners in 1998, 2005 and 2007 - are the $2.62 favourites at bet365, with Arsenal paying $2.75 while the draw at 90 minutes looks tempting at $3.60.
However there is a definite chance of upsets elsewhere with Championship sides Burnley, Leicester and Birmingham all at home to struggling EPL sides in West Ham, Fulham and Stoke respectively.
Burnley are currently leading the Championship and were semi-finalists in this competition as recently as 2009.
They are the narrow $2.62 favourites at home against the Hammers paying $2.80 at bet365 while the draw at 90 minutes is paying $3.50.
Both teams are paying $1.83 in the 'To Qualify' market but with West Ham boasting just two wins from their past eight matches overall, we would much rather back the home side to eventually prevail.
But with the Hammers having kept six clean sheets from their past 11 games this match will be tight and the $1.95 on offer at bet365 on their being less than 2.5 goals scored in the 90 minutes looks the bet of the night while a 0-0 draw at 90 minutes is tempting at odds of $11.
Leicester won this competition in 1997 and 2000 and sit second in the Championship while Fulham are 14th in the EPL.
The Foxes are the $2.30 favourites at bet365 with Fulham paying $3.20 and the draw $3.60.
Incredibly Leicester have won their past five home games in all competitions by the same score line - 2-1 - and they are a tempting $9 at bet365 to win by that score again on Tuesday night against a Fulham side that needed penalties to win away against lowly Burton Albion in the second round.
Birmingham sit a disappointing 20th in the Championship although they face a Stoke side sitting just above the relegation zone in 17th spot in the EPL.
But the Blues are a different side when it comes to this competition and scored a shock win over Arsenal in the 2011 final and were unlucky to be beaten on penalties in the 2001 final by Liverpool.
And Stoke have only won away once in the EPL this season although they did beat Tranmere away from home in the third round in this competition.
But they still look a risk at $2.10 with bet365 compared to $3.80 for the home side while the draw at 90 minutes is paying $3.50.
However the safer option might be to take Birmingham at $2.50 in the To Qualify market meaning the home side can also clinch victory in extra time or on penalties.
In the final game Manchester United should win at home at $1.33 against struggling Norwich at $11 despite their stuttering start to the EPL season.
United, winners of this competition in 2006, 2009 and 2010, are also the $5 favourites to win the competition this season at bet365 - ahead of the fourth round.
Then comes Tottenham at $5.50 followed by Manchester City at $6, Arsenal and Chelsea both at $8 and Southampton at $15.
*Note prices subject to change