Pogačar was the fastest over a mostly flat course that was expected to suit the time trial specialists in the field. The Slovenian showed that he continues to save his best form for Tour de France time trials, putting out a ride reminiscent of his heroics in the penultimate stage of last year's race.
The 22-year-old stopped the clock with a time of 32 minutes flat, averaging 51 km/hr over the course, finishing 19 seconds ahead of Stefan Küng (Groupama-FDJ) with Jonas Vingegaard (Jumbo-Visma) finishing third, 27 seconds behind.
“Today was a really good day for me," Pogačar said. "It was just a really good day today. I didn't do any mistakes. It was perfect weather for me but sadly some guys went out on wet roads. I had perfect conditions and perfect temperature.
"I checked the course. In the last few time trials I did mistakes after starting super fast. I paced myself pretty good and found a perfect rhythm to the end.
"The goal was not to lose the time, but I gained time so I'm super happy. I'm just excited for the whole Tour. I would love to have the yellow jersey but Mathieu looks super nice, so it's fine.”
A battling effort from Mathieu van der Poel (Alpecin-Fenix) saw the star Dutchman maintain his hold on the yellow jersey, limiting his losses to Pogačar to just maintain his lead. He now holds an eight second lead in the general classification.
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Harry Sweeny (Lotto Soudal) set the early pace as the Aussie set the initial fastest time at the finish. His time wasn't to last too long however, as Mikkel Bjerg (UAE Team Emirates) swept home after setting fast marks at all the checkpoints out on course to post the fastest time, one that would prove a good marker for riders to follow.
His time was passed by Matteo Cattaneo (Deceuninck-QuickStep) before Küng blitzed home with his ride, stopping the clock at 32.19.
Australian Richie Porte (INEOS Grenadiers) showed that his form is still very strong despite losing time through misadventure in the opening stages, placing in the provisional top three, eventually finishing ninth on the day.
Primož Roglič (Jumbo-Visma) shrugged off the significant damage sustained in his Stage 3 fall, rebounding with a very strong time that saw him take time on many of his rivals for the final general classification.
Pogačar's blistering ride set the standard from then on as Wout van Aert (Jumbo-Visma) and Mathieu van der Poel (Alpecin-Fenix) fought to stay ahead on the general classification and vie for the yellow jersey.
Van Aert couldn't maintain the pace of his Slovenian rival, and while van der Poel looked to be struggling with his position at times, he dug deep up the final climb to produce his best-ever time trial showing and finish within the required 38-second deficit to Pogačar to maintain his hold on the overall race lead.
The Tour de France continues with Stage 6, a flat 160-kilometre stage from Tours to Châteauroux, a stage expected to finish with a bunch sprint. Watch the action on SBS, the SKODA Tour Tracker and SBS OnDemand from 2130 AEST.