Code:
        

Dim xmlPisac As New Xml.XmlTextWriter("c:\neki_fajl.xml", System.Text.Encoding.Default)

        With xmlPisac
            .Formatting = Xml.Formatting.Indented
            .Indentation = 4

            .WriteRaw("<?xml version=""1.0""?>")
            .WriteComment("Poslovni Adresar BiH")
            .WriteComment("www.adresar.ba")

            .WriteStartElement("Pocetak")

                .WriteStartElement("Naziv")
                .WriteStartElement("Test Program")
                .WriteEndElement()

                .WriteStartElement("Verzija")
                .WriteString("2.0")
                .WriteEndElement()

            .WriteEndElement()
        End With
        xmlPisac.Close()

Code:

        Dim xmlDoc As New Xml.XmlDocument
        Dim xmlNav As Xml.XPath.XPathNavigator
        Dim xmlIter As Xml.XPath.XPathNodeIterator
        Dim _naziv,_verzija as string

        xmlDoc.Load("c:\neki_fajl.xml")
        xmlNav = xmlDoc.CreateNavigator
        xmlIter = xmlNav.Select("Program")
        xmlIter.Current.MoveToFirstAttribute()

        While xmlIter.MoveNext
            Do
                xmlIter.Current.MoveToFirstChild()
                Do


                    Select Case xmlIter.Current.Name
                        Case "Naziv" : _naziv = xmlIter.Current.Value
                        Case "Verzija" : _verzija = xmlIter.Current.Value
                    End Select

                Loop Until (Not xmlIter.Current.MoveToNext)
            Loop Until (Not xmlIter.Current.MoveToNextAttribute)
        End While

Code:

            XmlDocument xmlDoc = new XmlDocument();
            string _verzija;
            xmlDoc.Load("test.xml");
            _verzija = xmlDoc.SelectSingleNode("//Program/Verzija").InnerText;