Assuming there your Excel file consists of a single column with email adresses only, I would save as csv, and then read that file from perl, using a combination of the advice above.
As a side-note, you may want to validate your email adresses as described in perlfaq9.
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print map{chr}unpack(q{A3}x24,q{074117115116032097110111116104101114032080101114108032104097099107101114})
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Mail::Sendmail contains a regex to check for valid addresses that's pretty good, although not complete in a mathematically exhaustive way.
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