The Clarets frontman has netted four times already in the Premier League this season, but was overlooked by Gareth Southgate for the upcoming Euro qualifiers against Bulgaria and Kosovo.
Barnes, who was born in Bath to English parents, has represented Austria at youth level before, but would still be eligible for the Three Lions.
He failed with an application for Austrian citizenship in February earlier this year, so England no longer have to compete for his allegiance.
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At 29 and without any international experience, some would suggest Barnes has missed the boat, but Pearce insists Southgate will pick players based solely on form.