One PO can not have different vendors. Its logical as one PO goes to one vendor with address.
You cannot change the Vendor once you have saved the Purchase Order. SAP treats the Purchase Order as a legal document. Therefore, once the Purchase Order is saved, it will not let you change the vendor.
You have to delete all the line items and then create another Purchase Order. However, if you are using Enjoy Purchase Order, you can "Hold" the Purchase Order rather than save it after you have create it, then you can change the vendor.
Of course, this means that you don't have any output yet. Therefore, you are not bounds by a legal document as you have not given it to a specific supplier yet.
Logically, you cannot change an important field after creating a document. It defeats the RDBMS principle, but you can change vendor while doing Invoice Verification.
No, you cannot change vendor in released PO, because vendor registration carries some vital configuration information which decides pricing procedure for the items of the PO, logically due to this reasons system doen't allow to change vendor name once PO is released.
Normal practise to come out for this routine problem in purchasing is solved by, simply delete this PO (By changing delivery as completed in PO) and make a new PO for these items.
Eventually, you have only two options:
1. You can do the entire transaction with that wrong vendor number and after MIRO you can transfer post the vendor liability to correct vendor through FI route. BUT THIS IS A WRONG PRACTICE.
2. You need to cancel the PO which has wrong vendor number and create it again with correct vendor code
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