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Private Sub Form1_Load(ByVal sender As System.Object, ByVal e As System.EventArgs) Handles MyBase.Load
    Dim strData() As String = {"A", "B", "D", "E"}
    'コンボボックスにアイテムを追加する
    ComboBox1.Items.AddRange(strData)
End Sub

Private Sub Button1_Click(ByVal sender As System.Object, ByVal e As System.EventArgs) Handles Button1.Click
    '"C"を"B"の後ろに挿入します
    ComboBox1.Items.Insert(2, "C")
End Sub