The England skipper's opposite number, Manuel Neuer, has worn the armband in every match his side have played in June in honour of Pride Month.
The Germany goalkeeper first wore the rainbow armband against Latvia on June 7 and then during his country's three Group F matches against France, Portugal and Hungary.
In a tweet, England said: "Harry Kane will join Germany's Manuel Neuer in wearing a rainbow captain’s armband for tomorrow’s game at Wembley Stadium to mark the end of Pride month, as the Three Lions stand in allyship with LGBTQ+ communities around the world."
Uefa previously investigated whether it could be viewed as a political statement before concluding there would be no disciplinary proceedings, given Neuer was "promoting a good cause".
❤️🧡💛💚💙💜@HKane will join @DFB_Team's Manuel Neuer in wearing a rainbow captain’s armband for tomorrow’s game at @wembleystadium to mark the end of Pride month, as the #ThreeLions stand in allyship with LGBTQ+ communities around the world. pic.twitter.com/ML8yEnz6Gn
— England (@England) June 28, 2021
The governing body then denied a request by Munich mayor Dieter Reiter for the Allianz Arena to be lit up in rainbow colours when Germany played Hungary there on Wednesday.
The last-16 clash on Tuesday will be the first time Kane will don the armband, which is in support of LGBTQ+ communities.
Additional reporting by the Press Association.