Yes. If they are still legally married and he does not maintain a home for a qualifying dependent that would qualify him to file as Head of Household, then his only filing status option would be Married Filing Separately.
No. If she itemizes he does not have to. Since she is filing HOH, she is considered unmarried for tax purposes so the matching rule does not apply. So he can take the standard deduction or itemized deduction.
Which state do they live in? If they live in a community property state, the rules may be slightly different as to how it works for her to file HOH and him to file MFS. They still may have to allocate income and expenses depending on which state they live in.
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