Just add ELSE and then what you want it to do

Public Sub CreateHypersFromCells()
Dim vFile, vName, vVendor, vDate, vInvoice
Const kDIR = "c:\temp\"

Range("A2").Select
While ActiveCell.Offset(0, 1).Value <> ""
   
      'use path in cell to create hyperlink
   vVendor = ActiveCell.Offset(0, 1).Value
   vInvoice = ActiveCell.Offset(0, 3).Value
   
   vFile = kDIR & vVendor & vInvoice & ".pdf"
   
   'If FileExists(vFile) Then
      ActiveSheet.Hyperlinks.Add Anchor:=Selection, Address:=vFile, TextToDisplay:=vFile
   'ELSE
     ' SPECIFY HERE WHAT YOU WANT IT TO DO
   'End If
   
   ActiveCell.Offset(1, 0).Select  'next row
Wend

End Sub