Both were in outstanding touch as they hunt for more Grand Slam glory with Djokovic meeting defending champion Stanislas Wawrinka for a place in the final while Serena will face unseeded Madison Keys.
Big-serving Canadian eighth seed Raonic had no answer to Djokovic's superior all-court game and was ruthlessly swept aside 7-6 (7/5), 6-4, 6-2, surrendering meekly after just two hours.
"I'm going to be ready for a fight against Wawrinka," said the Serb, gunning for an eighth Grand Slam title and a fifth in Melbourne. "But knowing that I have raised the level of performance tonight is affecting my confidence in a positive way."
Serena was equally impressive, shooting down last year's finalist Cibulkova to set up a revenge clash with fellow American Keys, who knocked out her sister Venus.
The powerful 33-year-old blasted 15 aces to pummel the 11th seed 6-2, 6-2 in just over an hour and make her 26th Grand Slam semi-final.
"I feel I played well, I felt I had to," said Serena, who has been battling a cold. "I feel like when you're going up against a player like that who is confident on the court ... I knew that I needed to really play well or go home."
Keys unlocks debut Grand Slam last-four door
The unseeded Keys, 19, is the tournament surprise package, fighting hard to beat a resurgent Venus 6-3, 4-6, 6-4 and end any chance of the sisters meeting in a Grand Slam semi for the first time since Wimbledon 2000.
Keys did the job despite inconvenienced by a left thigh injury.
In an ominous sign for Keys, Serena has made the last four in Melbourne five times before and gone on win the championship each time.
But Keys, coached by former Australian champion Lindsay Davenport, is undaunted. "It's just one of those things where I have to go out and I have to do my best and I have to really just stay focused on my side of the court," she said.
Serena’s arch-rival Maria Sharapova made the semis on Tuesday and will face fellow Russian Ekaterina Makarova today.
Wawrinka on course to defend title
Wawrinka shattered the dream of Japanese superstar Kei Nishikori, but not before blowing five match points in a tiebreaker as nerves got the better of him.
The Swiss fourth seed finally won 6-3, 6-4, 7-6 (8/6) to deprive the fifth seed of a crack at another final, having made the US Open decider last year.
"I trust my game. I trust myself on the court even when we start to play semi-final or final in Grand Slam," he said of meeting Djokovic.
Andy Murray and Tomas Berdych play the other semi-final after booking their places on Tuesday.
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Lindsay Ann Davenport is a former World No. 1 American professional tennis player. Not Australian.