De Bruyne had scored one goal and made two in Saturday's 3-1 win over Southampton and he continued in the same vein as the 2014 winners saw off second-tier Hull, with Wilfried Bony and Kelechi Iheanacho also scoring.
Gerard Deulofeu starred as Everton won 2-0 at Middlesbrough and Stoke City beat Sheffield Wednesday 2-0 to guarantee an all-Premier League last four ahead of Liverpool's trip to Southampton on Wednesday.
"We only had 72 hours to recover (from the game against Southampton) so it was a very good answer from all the squad," said City manager Manuel Pellegrini.
"The most important thing is to be involved in all the competitions at this stage. We were very solid and we didn't allow chances for Hull to score."
City made five changes for the visit of Hull, currently fourth in the Championship, with David Silva captaining the side at the Etihad Stadium on his first start following two months out with an ankle problem.
Sergio Aguero was absent, having taken a knock in the win over Southampton, but Bony ensured that he was not missed by following in to open the scoring in the 12th minute after De Bruyne had hit the post.
Pellegrini said afterwards that Aguero and goalkeeper Joe Hart, who also missed out against Hull, could return at Stoke on Saturday.
Iheanacho replaced Bony in the 71st minute and got on the score-sheet nine minutes later, toeing in a cross from Raheem Sterling.
De Bruyne's brace arrived late on, the Belgium forward exploiting a defensive mistake to prod home in the 82nd minute and then sweeping a free-kick into the top-left corner three minutes from time.
Andrew Robertson tucked away an injury-time consolation for Hull.
Everton defeated Middlesborough to qualify for the semi-finals.
© AFP
- Deulofeu dazzles -
Former Barcelona winger Deulofeu stole the show as Everton won at Championship high-fliers Middlesbrough, who had eliminated Manchester United on penalties at Old Trafford in the fourth round.
The 21-year-old Spaniard broke the deadlock in the 20th minute at the Riverside Stadium, wriggling between two defenders and shaping a low shot into the bottom-left corner from the edge of the box.
Eight minutes later he set up Everton's second goal, bamboozling Fernando Amorebieta with a flurry of step-overs and crossing for Romelu Lukaku to head in his 13th goal of the season, and sixth in five games.
"Playing with Romelu Lukaku is easy for me," said Deulofeu, whose club have never won the League Cup.
"I am so happy to reach the next round and want to keep going."
Everton manager Roberto Martinez told Sky Sports: "It is a terrific feeling to get through to the semi-final and a good memory for our football club."
The 21-year-old Spaniard broke the deadlock in the 20th minute at the Riverside Stadium, wriggling between two defenders and shaping a low shot into the bottom-left corner from the edge of the box.
Eight minutes later he set up Everton's second goal, bamboozling Fernando Amorebieta with a flurry of step-overs and crossing for Romelu Lukaku to head in his 13th goal of the season, and sixth in five games.
"Playing with Romelu Lukaku is easy for me," said
Deulofeu, whose club have never won the League Cup.
"I am so happy to reach the next round and want to keep going."
Everton manager Roberto Martinez told Sky Sports: "It is a terrific feeling to get through to the semi-final and a good memory for our football club."
Championship side Wednesday had stunned Arsenal 3-0 in the previous round, but their cup adventure came to an end at Stoke's Britannia Stadium.
Peter Crouch limped off with an apparent hamstring injury in the early stages, but his replacement, Joselu, teed up Ibrahim Afellay to volley in Stoke's opener on the half hour.
Full-back Phil Bardsley wrapped up the win with 15 minutes to play by driving home from a free-kick as Stoke reached the last four for the first time since they won the tournament in 1972.
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