Sure -- here is the default template for ScrollViewer
modified to transpose grid row 0 and grid row 1, which puts the horizontal scroll bar at the top:
<ControlTemplate x:Key="ScrollViewerHorizontalOnTopTemplate" TargetType="{x:Type ScrollViewer}">
<Grid x:Name="Grid" Background="{TemplateBinding Background}">
<Grid.ColumnDefinitions>
<ColumnDefinition Width="*"/>
<ColumnDefinition Width="Auto"/>
</Grid.ColumnDefinitions>
<Grid.RowDefinitions>
<RowDefinition Height="Auto" MinHeight="17"/>
<RowDefinition Height="*"/>
</Grid.RowDefinitions>
<Rectangle x:Name="Corner"
Fill="{DynamicResource {x:Static SystemColors.ControlBrushKey}}"
Grid.Column="1" Grid.Row="0"/>
<ScrollContentPresenter x:Name="PART_ScrollContentPresenter" Margin="{TemplateBinding Padding}" Content="{TemplateBinding Content}" ContentTemplate="{TemplateBinding ContentTemplate}" Grid.Column="0" Grid.Row="1" CanContentScroll="{TemplateBinding CanContentScroll}" CanHorizontallyScroll="False" CanVerticallyScroll="False"/>
<ScrollBar x:Name="PART_VerticalScrollBar"
Cursor="Arrow"
Visibility="{TemplateBinding ComputedVerticalScrollBarVisibility}"
Grid.Column="1" Grid.Row="1"
AutomationProperties.AutomationId="VerticalScrollBar"
Maximum="{TemplateBinding ScrollableHeight}"
Minimum="0"
Value="{Binding VerticalOffset, Mode=OneWay, RelativeSource={RelativeSource TemplatedParent}}"
ViewportSize="{TemplateBinding ViewportHeight}"/>
<ScrollBar x:Name="PART_HorizontalScrollBar"
Cursor="Arrow"
Grid.Column="0"
AutomationProperties.AutomationId="HorizontalScrollBar"
Maximum="{TemplateBinding ScrollableWidth}"
Minimum="0"
Value="{Binding HorizontalOffset, Mode=OneWay, RelativeSource={RelativeSource TemplatedParent}}"
Orientation="Horizontal"
ViewportSize="{TemplateBinding ViewportWidth}"/>
</Grid>
</ControlTemplate>
Apply this template to your ScrollViewer
and you should be all set.
Expression Blend makes tasks like this trivial -- I recommend it.