Video report by ITV News Correspondent Amy Lewis
The online charity concert will see the 46-year-old and his former bandmates Gary Barlow, Mark Owen and Howard Donald each perform from their own respective homes.
The band are getting back together on Friday night for a performance in aid of music therapy charity Nordoff Robbins, and Crew Nation, which supports concert crew workers.
It will be the first time Williams has performed with the band since the 2018 X Factor final, where they sang Shine.
Williams told The Sun: "I am really looking forward to performing with the boys again - it's always a pleasure. If we can't go to the stadium... we'll bring the stadium to us."
In April, Williams and Barlow performed a virtual duet of their 2010 song Shame from their homes.
Alongside the video, Gary wrote: "Sorry to have made you wait so long for this one. Yes the dynamic duo return."
"Thank you Robbie Williams for taking the time to be part of this. Big hugs (virtually of course) #thecroonersessions," he added.
The Take That stars tweeted a video of themselves performing the number as a part of Barlow's "crooner sessions" - a series of performances recorded by singers remotely during the lockdown.
The pair co-wrote Shame together for Robbie's second greatest hits album, In and Out of Consciousness: Greatest Hits 1990-2010.
The song was the first time the pair collaborated on a song together solely and it was also the first time they had worked together since Robbie left Take That in 1995.
Fans have been looking forward to the special concert on Friday night, which will be broadcast by comparethemarket.com, and is being billed as the debut Meerkat Music event to boost morale amid the ongoing pandemic.
The gig will be broadcast on the Meerkat Music YouTube channel from 8pm.
They will perform their hits Greatest Day, Shine, Back For Good, The Flood, Pray, Never Forget; and then two extra songs, Everything Changes and Rule The World, which will be available to the website's customers only.
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