Saved from a previous post:

Using the pagebreak view of a newly created workbook doesn't make a lot of sense
to me.

Try it to see what it does.  I wouldn't use it.

But this will do what you ask (both opening existing workbooks and creating new
workbooks).

Start a new workbook
copy this code into the ThisWorkbook module.

Option Explicit
Public WithEvents xlApp As Excel.Application
Private Sub Workbook_Open()
   Set xlApp = Application
End Sub
Private Sub Workbook_Close()
   Set xlApp = Nothing
End Sub
Private Sub xlApp_NewWorkbook(ByVal Wb As Workbook)
   Dim myWindow As Window
   For Each myWindow In Wb.Windows
       myWindow.View = xlPageBreakPreview
   Next myWindow
End Sub
Private Sub xlApp_WorkbookOpen(ByVal Wb As Workbook)
   Dim myWindow As Window
   For Each myWindow In Wb.Windows
       myWindow.View = xlPageBreakPreview
   Next myWindow
End Sub

Now save this workbook in your XLStart folder.

Then close excel and restart excel.

If you don't want the new workbook to be affected, just delete this portion:

Private Sub xlApp_NewWorkbook(ByVal Wb As Workbook)
   Dim myWindow As Window
   For Each myWindow In Wb.Windows
       myWindow.View = xlPageBreakPreview
   Next myWindow
End Sub

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If you're new to macros, you may want to read David McRitchie's intro at:
http://www.mvps.org/dmcritchie/excel/getstarted.htm

And you can read a lot more about application events at Chip Pearson's site:
http://www.cpearson.com/excel/AppEvent.htm