I suggest moving your ComboBox outside of the DataTemplate, and do your ComboBox customisation inside an ItemTemplate.
<Window x:Class="BindXML.Views.MainView"
xmlns="http://schemas.microsoft.com/winfx/2006/xaml/presentation"
xmlns:x="http://schemas.microsoft.com/winfx/2006/xaml"
Title="Main Window" Height="400" Width="800">
<Window.Resources>
<DataTemplate x:Key="comboTemplate">
<TextBlock Text="{Binding XPath=@ImageName}" Width="70" />
</DataTemplate>
<XmlDataProvider x:Key="src" XPath="/Root">
<x:XData>
<Root xmlns="">
<Item ImageName="Image1.jpg" />
<Item ImageName="Image2.jpg" />
<Item ImageName="Image3.jpg" />
</Root>
</x:XData>
</XmlDataProvider>
</Window.Resources>
<DockPanel>
<Grid>
<Grid.RowDefinitions>
<RowDefinition/>
<RowDefinition/>
<RowDefinition/>
</Grid.RowDefinitions>
<ComboBox x:Name="cboImages1"
Grid.Row="0"
DataContext="{StaticResource src}"
ItemTemplate="{StaticResource comboTemplate}"
ItemsSource="{Binding XPath=Item}"
SelectedItem="{Binding XPath=ImageName, Path=SelectedItem.Content, Mode=TwoWay}"
IsSynchronizedWithCurrentItem="True" >
</ComboBox>
<ComboBox x:Name="cboImages2"
Grid.Row="1"
DataContext="{StaticResource src}"
ItemTemplate="{StaticResource comboTemplate}"
ItemsSource="{Binding XPath=Item}"
SelectedItem="{Binding XPath=ImageName, Path=SelectedItem.Content, Mode=TwoWay}"
IsSynchronizedWithCurrentItem="True" >
</ComboBox>
<Button Grid.Row="2" Click="Button_Click" />
</Grid>
</DockPanel>
</Window>
The following test code-behind shows different ComboxBox selected items:
private void Button_Click(object sender, RoutedEventArgs e)
{
XmlElement e1 = cboImages1.SelectedItem as XmlElement;
if ( e1 != null )
{
XmlAttribute result1 = e1.Attributes["ImageName"] as XmlAttribute;
if ( result1 != null )
{
string name1 = result1.Value;
}
}
XmlElement e2 = cboImages2.SelectedItem as XmlElement;
if ( e2 != null )
{
XmlAttribute result2 = e2.Attributes["ImageName"] as XmlAttribute;
if (result2 != null)
{
string name2 = result2.Value;
}
}
}