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There are some people who aren't eligible to use the standard deduction.
Most importantly, if you are married and filing separately from your spouse, and one of you itemizes deductions, the other must itemize as well or use a standard deduction of zero. This is the IRS's way of making sure you don't abuse the situation by having one spouse claim all the itemized deductions for the couple, while the other spouse claims a full standard deduction.
Others who can't use the standard deduction are: