Hi

I can reproduce the scenario with your code.
ofile.Copy will throw exception on my side because of the destination path
is not existing.

Here is my test code which works file on my side.
I add the code line below to ensure the destination path existed.
                   If Not Directory.Exists(path) Then
                       Directory.CreateDirectory(path)
                   End If

You may have a try.

Imports System.IO
Module Module1
   Sub Main()
       Dim ofile As File
       Dim odir As Directory
       Dim owriter As StreamWriter
       Dim dirlist1 As String() = odir.GetDirectories("C:\Documents and
Settings\user\My Documents")
       Dim list As String
       Dim str As String
       Dim i As Integer
       Dim chararr As String()
       Dim attrib As FileAttributes
       Dim array As String()

       For Each list In dirlist1
           array = odir.GetFiles(list)
           For Each str In array
               attrib = ofile.GetAttributes(str)
               If attrib = 32 Then
                   chararr = str.Split("\")
                   i = chararr.Length - 1
                   Dim path As String = "C:\backupdir\" &
list.Replace("C:\Documents and Settings\user\", "")
                   Dim filepath As String = path & "\" & chararr(i)
                   If Not Directory.Exists(path) Then
                       Directory.CreateDirectory(path)
                   End If
                   Debug.WriteLine("Copy from " & str & " to " & filepath)
                   ofile.Copy(str, filepath)
                   ofile.SetAttributes(str, FileAttributes.Normal)
               Else
               End If
           Next
       Next
       Console.WriteLine("Finished.")
       Console.ReadLine()
   End Sub
End Module

Best regards,

Peter Huang
Microsoft Online Partner Support