Both were in outstanding touch as they hunt for more Grand Slam glory with Djokovic meeting defending champion Stan Wawrinka for a place in the final while Williams 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 Stan," said the Serb, gunning for an eighth Grand Slam title and a fifth in Melbourne.
Williams 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.
Unlike her earlier sluggish matches, Serena was in the zone from the off against the dangerous Slovak, a steely look in her eyes.
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. She has gone on to win 18 major titles.
"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."
Arch-rival Maria Sharapova made the semis on Tuesday and will face fellow Russian Ekaterina Makarova on Thursday.
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.
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