Pogacar prevailed in the final time trial to effectively secure his triumph last year and proved his prowess in the format again to surge up the general classification standings.
The riders had to deal with wet conditions along the 27.2 kilometre route from Change to Laval but Pogacar handled them superbly to top the timesheets.
Pogacar won three stages during last year’s race and secured his first success of 2021 with a time of exactly 32 minutes.
It was one nobody could get close to, with Stefan Kung 19 seconds adrift in second and Jonas Vingegaard a further eight back.
But Van der Poel maintained his advantage in the GC as he took fifth place behind Wout van Aert.
The Alpecin-Fenix rider was 31 seconds off the pace but his overall lead remains eight seconds, as it was after stage four.
However, Pogacar is now the man in second place, replacing home hope Julian Alaphilippe, who finished a minute and 11 seconds behind Pogacar in 14th.
Stage six, a 160.6km ride from Tours to Chateauroux, is likely to be one for the sprinters but Van der Poel, the winner of the only mountain stage so far, should have high hopes of doing more damage on stage seven when things will again favour the climbers.
STAGE RESULT
1. Tadej Pogacar (UAE Team Emirates) 32:00 2. Stefan Kung (Groupama-FDJ) +00:19 3. Jonas Vingegaard (Jumbo-Visma) +00:27 4. Wout van Aert (Jumbo-Visma) 5. Mathieu van der Poel (Alpecin-Fenix) +00:31
CLASSIFICATION STANDINGS
General Classification 1. Mathieu van der Poel (Alpecin-Fenix) 16:51:41 2. Tadej Pogacar (UAE Team Emirates) +00:08 3. Wout van Aert (Jumbo-Visma) +00:30
Points Classification 1. Mark Cavendish (Deceuninck-Quick-Step) 89 2. Julian Alaphilippe (Deceuninck-Quick-Step) 84 3. Mathieu van der Poel (Alpecin-Fenix) 78
King of the Mountains 1. Ide Schelling (Bora-Hansgrohe) 5 2. Mathieu van der Poel (Alpecin-Fenix) 4 3. Anthony Perez (Cofidis) 3
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