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.
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The Germany goalkeeper first wore the rainbow armband against Latvia on June 7 and then during his country’s three group matches against France, Portugal and Hungary.
UEFA 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”.
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.
When do England play Germany?
England will compete in the Euros Round of 16 which has fixtures taking place from Saturday 26 June to Tuesday 29 June.
England will play Germany at Wembley on Tuesday 29 June (5pm).
The quarter finals take place on Friday 2 July and Saturday 3 July with the winners advancing to the semi finals on Tuesday 6 July and Wednesday 7 July.
Both semi finals and the final on Sunday 11 July (8pm) of Euro 2020 will take place at Wembley.