Ahead of the match in Macedonia, we take a look at five talking points.
UNITED'S SUSPENSION-HIT DEFENCE
One of the main headaches for United boss Jose Mourinho against his former club will be how to line up at the back
Eric Bailly will miss the match through suspension, having been hit by an extended ban for his sending-off in May's Europa League semi-final second leg against Celta Vigo
To make matters worse, Phil Jones has also been given a UEFA ban following his behaviour towards a doping control officer after the Europa League final triumph against Ajax
Mourinho has been trialling a three-man defence in pre-season and it will be interesting to see how he looks to contain Zinedine Zidane's men.
LUKAKU LOOKING FOR SUPER CUP REDEMPTION
United's big-money summer signing does not have particularly fond memories of this competition
Romelu Lukaku's last Chelsea appearance came in the 2013 Super Cup final against Bayern Munich - a match in which he came off the bench in Prague, only to see his decisive spot-kick saved in the shootout
Mourinho was the Blues boss that night and is now set to the give the Belgium international a chance to atone on his competitive United debut
Tuesday's game also gives Lukaku a chance to quieten those suggesting he struggles against the best teams.
MATIC READY FOR ACTION?
After a long pursuit of the Chelsea defensive midfielder, United got their man late last month as Nemanja Matic joined for an initial Â£35million
The 29-year-old swiftly got a chance in red for the first time, putting in an impressive 45-minute display in the Dublin friendly against Sampdoria
Matic is not only seen as key for defensive cover but to unlocking Paul Pogba's potential, but whether the midfielder is ready for the rigours of facing the continent's best is in doubt.
Real Madrid have their own fitness concerns to deal with
Cristiano Ronaldo has only just returned to the group following his part in Portugal's Confederations Cup campaign and then appearing at a Spanish court
The 32-year-old has denied he evaded tax or hid details of his income from the authorities - charges that led the world's best player to seriously consider a move away from the Bernabeu earlier in the summer
However, Ronaldo appears set to stay put and has been included in the 24-man squad taking on former club United in Skopje
Whether he is ready to play a major part, though, remains to be seen.
The capital of Macedonia is abuzz with activity ahead of its first UEFA club competition final
The locals are lapping up the big-name visitors to Skopje, along with temperatures that have regularly soared above 40 degrees Celsius
It is forecast to be 36C when Mourinho's United side train at the National Arena Filip II on Monday - and a repeat of those temperatures for the Super Cup itself would see cooling breaks implemented
UEFA's match delegate will take into account other factors as well as the temperature measured 90 minutes before kick-off, namely how conditions will change as the evening continues.
Source : PA