Napoli will enter the contest off the back of a thumping 4-0 victory over Lecce in Serie A, while Real Madrid were 3-0 winners over Girona in La Liga last time out.
Match preview
Napoli have been far from perfect in Serie A this season, but they picked up their fourth league win of the campaign on Saturday by putting four unanswered goals past Lecce, with the result moving them onto 14 points from seven games.
Rudi Garcia's side are third in the Serie A table, four points behind leaders Inter Milan, while they have won three of their last four matches in all competitions, including a 2-1 success over Braga in their Champions League opener.
Braga actually levelled the scores at 1-1 in the 84th minute of the clash on September 20, but an own goal from Sikou Niakate in the 88th minute allowed Napoli to begin their 2023-24 European campaign with an important win.
The Blues reached the quarter-finals of last season's Champions League, which proved to be their best-ever performance in the competition, and they will be expecting to get out of the group this season, with the two favourites in the section locking horns in this contest.
Napoli last met Real Madrid in the round of 16 in 2016-17, with the Spanish giants winning 3-1 both home and away to advance into the next stage of the competition courtesy of a 6-2 aggregate success.
Real Madrid, who have won 14 European Cups, have been in strong form at the start of the 2023-24 campaign, suffering just one defeat, which came away to their bitter rivals Atletico Madrid last weekend.
Carlo Ancelotti's side have otherwise won every match, including seven in La Liga, with a total of 21 points leaving them at the top of the division, and they have responded impressively to the loss in the Madrid derby by beating Las Palmas and Girona, scoring five times and conceding zero.
Los Blancos were far from their free-flowing best against Union Berlin in their Champions League opener on September 20, but they managed to secure all three points courtesy of a 94th-minute effort from Jude Bellingham.
Real Madrid have actually won each of their last eight matches against Serie A opposition, while they have been victorious in 14 of their last 15 games against Italian clubs.
The capital outfit have only managed to win seven of their last 23 away games in the Champions League, though, suffering eight defeats in the process, which should hand Napoli confidence.
Real Madrid's immense history in this competition means that they cannot be underestimated when it comes to this season's trophy, and it would be a shock if they did not advance deep into the tournament once again.
Napoli Champions League form:
W
Napoli form (all competitions):
L
D
W
D
W
W
Real Madrid Champions League form:
W
Real Madrid form (all competitions):
W
W
W
L
W
W
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Team News
Napoli are currently without the services of three first-team players through injury, with Juan Jesus, Amir Rrahmani and Pierluigi Gollini on the sidelines for the Italian outfit.
The absences of Jesus and Rrahmani are big ones, but the home side did not suffer any fresh issues in their league success over Lecce on Saturday afternoon.
Victor Osimhen, who has five goals this season, and Matteo Politano will both return in the final third of the field, and there are not expected to be any major surprises when it comes to the home side's XI for this contest.
As for Real Madrid, Eder Militao, Thibaut Courtois and Arda Guler remain unavailable for selection, while a late check will need to be made on the fitness of David Alaba.
The Austrian was forced off against Las Palmas last week due to a groin issue, which saw him miss out against Girona, but Ancelotti said before Saturday's match that the defender could return against Napoli.
There are big decisions to be made all over the pitch, with Fran Garcia potentially being recalled at left-back, with Eduardo Camavinga moving into his usual midfield position.
Both Luka Modric and Toni Kroos might have to accept spots on the bench for this match, while Rodrygo is pushing to be recalled in the final third, with the Brazilian potentially starting alongside Vinicius Junior despite Joselu's impressive scoring form early in the campaign.
Napoli possible starting lineup:
Meret; Di Lorenzo, Ostigard, Natan, Olivera; Anguissa, Lobotka, Zielinski; Politano, Osimhen, Kvaratskhelia
Real Madrid possible starting lineup:
Kepa; Carvajal, Rudiger, Alaba, F Garcia; Camavinga, Tchouameni, Valverde; Bellingham; Rodrygo, Vinicius
We say: Napoli 1-1 Real Madrid
This has all of the makings of a fascinating match, and we are expecting a very close contest on Tuesday evening. A case could be made for either side to win it, but both managers will be desperate to avoid defeat, which could create a cagey affair, and we are expecting the spoils to be shared in Naples.