Override the control template for the treeview to change the border. If you have Expression Blend, it can extract the default control template for you easily and then you can simply slap the appropriate radius on the topmost border.
Alternately, take a look at this MSDN article which contains the following treeview control template:
<Style x:Key="{x:Type TreeView}" TargetType="TreeView">
<Setter Property="OverridesDefaultStyle" Value="True" />
<Setter Property="SnapsToDevicePixels" Value="True" />
<Setter Property="ScrollViewer.HorizontalScrollBarVisibility" Value="Auto"/>
<Setter Property="ScrollViewer.VerticalScrollBarVisibility" Value="Auto"/>
<Setter Property="Template">
<Setter.Value>
<ControlTemplate TargetType="TreeView">
<Border
Name="Border"
CornerRadius="1"
Background="{StaticResource WindowBackgroundBrush}"
BorderBrush="{StaticResource SolidBorderBrush}"
BorderThickness="1" >
<ScrollViewer
Focusable="False"
CanContentScroll="False"
Padding="4">
<ItemsPresenter/>
</ScrollViewer>
</Border>
</ControlTemplate>
</Setter.Value>
</Setter>
</Style>
Simply change the outer border to have a stronger border radius should achieve what you want.