The four-time Tour de France champion, who has been struggling to hit top form since returning from a career-threatening crash last year, will lead Ineos-Grenadiers alongside 2019 Giro d’Italia winner Richard Carapaz.
Froome will leave the team at the end of the season to join Israel-Start Up Nation.
Jumbo-Visma will go with former Giro champion Tom Dumoulin and this year’s Tour de France runner-up Primož Roglič after the Slovenian lost the overall lead on cycling's biggest stage on the last competitive day.
“During the Vuelta," Jumbo-Visma sports director Grischa Niermann said. "It will become clear who will be our main man.
"Our team is at the start with two favourites for the final victory, one of them is last year’s winner."
Esteban Chaves will lead Mitchelton-Scott's squad containing Grand Tour debutants, Aussies Callum Scotson and Robert Stannard. The Colombian will aim for a strong overall placing while Mikel Nieve and Dion Smith will provide options for stage wins.
"I'm very happy to do the Vuelta this year," Chaves said. "It’s one race that I have a lot of appreciation for, I really like to do this race and enjoy it.
"This year, because of the timing of the race and the circumstances, like everything I feel a bit weird.
"But I feel like I am arriving in good condition especially after the Tour and world championships.
“We will race hard from the beginning; it is really hilly and if you have good legs then you need to be aggressive and take any chances from the start."
Other challengers include France’s Thibaut Pinot (Groupama-FDJ), who lost all hope of winning the Tour after sustaining a back injury during the opening stage, but also Spaniard Enric Mas (Movistar), who finished the Vuelta in second place in 2018.
The Vuelta starts from Irun early Wednesday morning (AEDT).
The race will only feature 18 stages after organisers scrapped the start from the Netherlands amid the COVID-19 crisis.
Jumbo-Visma line-up: Primož Roglič, Tom Dumoulin, Lennard Hofstede, Jonas Vingegaard, George Bennett, Paul Martens, Robert Gesink, Sepp Kuss
Ineos Grenadiers line-up: Chris Froome, Andrey Amador, Richard Carapaz, Michał Gołaś, Dylan van Baarle, Brandon Rivera, Iván Ramiro Sosa, Cameron Wurf
Mitchelton-Scott line-up: Mikel Nieve, Esteban Chaves, Alexander Edmondson, Tsgabu Grmay, Dion Smith, Nick Schultz, Callum Scotson, Robert Stannard
How to watch the 2020 Vuelta a España LIVE on SBS:
Wednesday October 21 - LIVE
Vuelta a España – Stage 1
12am AEDT SBS VICELAND / Streaming to SBS On Demand
Thursday October 22 - LIVE
Vuelta a España – Stage 2
12:05am AEDT SBS VICELAND / Streaming to SBS On Demand
Friday October 23 - LIVE
Vuelta a España – Stage 3
12am AEDT SBS VICELAND / Streaming to SBS On Demand
Saturday October 24 - LIVE
Vuelta a España – Stage 4
12am AEDT SBS VICELAND / Streaming to SBS On Demand
Sunday October 25 - LIVE
Vuelta a España – Stage 5
12am AEDT SBS VICELAND / Streaming to SBS On Demand
Sunday October 25 - LIVE
Vuelta a España – Stage 6
10:55pm AEDT SBS VICELAND / Streaming to SBS On Demand
Wednesday October 28 - LIVE
Vuelta a España – Stage 7
12:35am AEDT SBS VICELAND / Streaming to SBS On Demand
Thursday October 29 - LIVE
Vuelta a España – Stage 8
12:35am AEDT SBS VICELAND / Streaming to SBS On Demand
Friday October 30 - LIVE
Vuelta a España – Stage 9
12:35am AEDT SBS VICELAND / Streaming to SBS On Demand
Saturday October 31 - LIVE
Vuelta a España – Stage 10
12:35am AEDT SBS VICELAND / Streaming to SBS On Demand
Saturday October 31 - LIVE
Vuelta a España – Stage 11
11pm AEDT SBS VICELAND / Streaming to SBS On Demand
Sunday November 1 - LIVE
Vuelta a España – Stage 12
11.45pm AEDT SBS VICELAND / Streaming to SBS On Demand
Wednesday November 4 - LIVE
Vuelta a España – Stage 13
12:40am AEDT SBS VICELAND / Streaming to SBS On Demand
Thursday November 5 - LIVE
Vuelta a España – Stage 14
12:40am AEDT SBS VICELAND / Streaming to SBS On Demand
Friday November 6 - LIVE
Vuelta a España – Stage 15
12:35am AEDT SBS VICELAND / Streaming to SBS On Demand
Saturday November 7 - LIVE
Vuelta a España – Stage 16
12:35am AEDT SBS VICELAND / Streaming to SBS On Demand
Saturday November 7 - LIVE
Vuelta a España – Stage 17
11pm AEDT SBS VICELAND / Streaming to SBS On Demand
Monday November 9 - LIVE
Vuelta a España – Stage 18
12:35am AEDT SBS VICELAND / Streaming to SBS On Demand
