38-year-old Ariel Hernandez, of the 3400 block of Ditman Street, was arrested around 4:20 p.m. Wednesday.
He is charged with attempt to commit rape, indecent assault and related offenses.
The female worker was reportedly assaulted while inside her mail truck in the 6900 block of Old York Road late Wednesday afternoon.
"We're going to come to the bottom of this and hold the individual accountable who is brazen enough to assault a hardworking postal employee," said U.S. Postal Inspector Reginald Wade.
The postal service says this type of crime on a letter carrier is not at all common.
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