Chelsea beat Esperance of Tunisia 3-0 on Tuesday to set up a Club World Cup last-16 tie against Benfica, who defeated Bayern Munich 1-0 earlier in searing heat.
Elsewhere minnows Auckland City claimed a memorable draw against Boca Juniors while Los Angeles FC bowed out of the tournament with a stalemate against Flamengo, AFP reported.
In Charlotte, Andreas Schjelderup scored the only goal for Benfica in their Group C clash with Bayern in front of 33,287 fans, finishing first-time from a cutback by his fellow Norwegian Fredrik Aursnes in the 13th minute.
The German champions, who left the likes of Harry Kane and Michael Olise on the bench at kick-off, were unable to come back in sweltering afternoon conditions in heatwave-hit North Carolina.
Kane and Olise came on at half-time and Bayern did then look more dangerous, but Leroy Sane was denied when clean through by Benfica's Ukrainian goalkeeper Anatoliy Trubin.
A draw would have allowed Bayern to top the section but a Kimmich effort that found the net was ruled out for offside and Trubin denied Sane again while Kane mistimed a header late on.
It was Benfica's first ever win in 14 competitive meetings with Bayern and it meant they finished first and will next play Group D runners-up Chelsea in Charlotte in the last 16 on Saturday.
"I think this was a very fair and important win, historic really," said Benfica coach Bruno Lage.
"We were as straightforward and assertive as we should be and I think we were very effective in delivering our strategy today."
Bayern finished second and so will go to Miami on Sunday to take on Brazilian giants Flamengo, with a potential quarter-final against European champions Paris Saint-Germain awaiting.
"You could see that it was really tough conditions so respect to both teams for that," said Bayern coach Vincent Kompany.
"Our first half was not good enough for sure, the second half was definitely more the level that we expected and good enough to score one or two or three goals."
That result meant whatever Boca did against Auckland City in Nashville would not be enough to qualify, but the Argentine giants were still expected to do better than draw 1-1 against the tournament minnows from New Zealand.
Auckland had lost 10-0 to Bayern and 6-0 to Benfica but this time they recovered from falling behind in the first half when goalkeeper Nathan Garrow palmed a Lautaro Di Lollo header into his own net.
Christian Gray equalized with a header in the second half to earn the sole representatives from Oceania a remarkable point.
"You can't say we haven't learned from the experience of being at the tournament, I'm thrilled for the players and the club, it's wonderful. It's something to go home with," said City coach Paul Posa.
"We're a tiny club with a huge heart and that's evident for all to see."
The game was the fifth so far at the tournament to be suspended due to a weather warning, with play stopping for almost an hour -- when the action restarted not a drop of rain had fallen at Geodis Park.
Chelsea eased through to their meeting with Benfica with a clinical 3-0 win over Esperance at Lincoln Financial Field in Group D in Philadelphia.
New signing Liam Delap opened his account for the club with a deftly-taken finish in stoppage time at the end of the first half, just moments after Tosin Adarabioyo had headed the Blues in front.
Teeenage talent Tyrique George added Chelsea's third deep into injury time at the end of the game with a low shot that crept under Esperance goalkeeper Bechir Ben Said.
Flamengo, who had already assured themselves of top spot in the section after wins over Chelsea and Esperance, wrapped up their first-round campaign with a 1-1 draw against already-eliminated LAFC in Orlando.
Los Angeles forward Denis Bouanga threatened to give the MLS side an upset win in their final game of the tournament after a cool finish in the 84th minute, only for Wallace Yan to equalize for Flamengo two minutes later.
