I am sorry. But at this time it is not possible to Sync anything from Outlook Express via USB cable.
Now if by chance this is an IMAP based account, and those same folders are on the central email server. Then when you set it up on iPhone yes it will copy over as part of the IMAP account.
This thread has been closed by the system or the community team.
You may vote for any posts you find helpful, or search the Community for additional answers.
Outlook Express Sync
Welcome to Apple Support Community
A forum where Apple customers help each other with their products. Get started with your Apple Account.