The forward had vital penalties saved against Everton and Leeds this season but told FourFourTwo that he'd immediately step up if Fabio Capello needed a penalty taker.
England have been eliminated in penalty shootouts at their last two major tournament appearances in 2004 and 2006.
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Speaking exclusively in the new issue of FourFourTwo - out today - the diminutive White Hart Lane hitman was adamant when asked if he'd put his hand up to take a penalty for England.
"Hell yeah, 100 percent!" insisted Defoe. "The penalty misses this season have been totally my fault.
"I hadn't practised them enough, I'd taken my eyes off penalties a little bit, and that's why I missed. If you don't practise regularly you can't expect to be great at something - you can't just turn these things off and on like a light.
"I'm practising now to try to correct that!"
Defoe is interviewed in the June issue ofFourFourTwo – out now. He discusses first-touch goals, gym work and becoming "a deep midfielder when I'm 40."
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