XML 設定ファイルを読み込んで Dictionary に設定する。

Visual Basic の Dictionary は Hash のようなものです。Smalltalk に Dictionary というのがりますので Smalltalk 由来かも知れません。
XML ファイル

<configure>
  <item>
    <key>hoge</key>
    <value>http://www.example.com</value>
  </item>
  <item>
    <key>Googel</key>
    <value>http://www.google.com</value>
  </item>
</configure>

Imports System
Imports System.Collections.Generic

Module Module1

    Sub Main()
        Dim DirName As String
        Dim XMLName As String = "sample.xml"
        Dim dSet As New DataSet
        Dim dTbl As DataTable
        Dim sRead As IO.StreamReader
        Dim openWith As New Dictionary(Of String, String)


        DirName = System.IO.Directory.GetCurrentDirectory()

        Try
            dSet.ReadXmlSchema(DirName + "\" + XMLName)
            sRead = New IO.StreamReader(DirName + "\" + XMLName, System.Text.Encoding.Default)
            dSet.ReadXml(sRead)
            dTbl = dSet.Tables(0)
            For i = 0 To dTbl.Rows.Count() - 1
                Try
                    openWith.Add(dTbl.Rows(i)(0), dTbl.Rows(i)(1))
                Catch
                    Console.WriteLine("An element with Key = " & dTbl.Rows(i)(0) & " already exists.")
                End Try
            Next
        Catch E As Exception
            System.Console.WriteLine(E.Message)
        End Try

        System.Console.WriteLine(openWith("hoge")) ' hoge の値を表示
        ' 全部表示
        For Each kvp As KeyValuePair(Of String, String) In openWith
            System.Console.WriteLine("Key = {0}, Value = {1}", kvp.Key, kvp.Value)
        Next kvp

    End Sub

End Module

結果

http://www.example.com
Key = hoge, Value = http://www.example.com
Key = Googel, Value = http://www.google.com