Could there actually be an invalid expression in the control source of one
of the calculated controls in the subform?
Could the LinkMasterFields and LinkChildFields properties of the subform
control be set incorrectly? Access will attempt to assign the values from
the main form's fields/controls (named in LinkMasterFields) to the subform's
field/controls (named in LinkChildFields) when you begin adding a record.
If neither of those apply, is the subform based on a query that contains
more than one table? If so, try removing anything in the Default Value of
any controls in the subform, and also remove the Default Value from all
fields in all tables this query is based on. I have seen an error (a
different one) at the precise timing you describe, and traced it back to the
fact that Access was attempting to apply the Default Value to the new record
when the Default Value was set on a field in the lookup table (not the table
the record was being appended to.) Removing the Default Value worked around
the bug.
Hopefully one of those ideas helps.