You cant bind this because you are trying to bind a string to an object which wont work because StringFormat requires its target to be a string type. You can get around this by either using a TextBlock instead (which has a Text property) or putting the Textblock as the child of the Label:
<Label x:Name="myLabel">
<Label.Content>
<TextBlock>
<TextBlock.Text>
<MultiBinding StringFormat="{}{0} - {1}">
<Binding Path="Lib1" />
<Binding Path="Lib2" />
</MultiBinding>
</TextBlock.Text>
</TextBlock>
</Label.Content>
</Label>