To set the value for alignment, you need to do something like this:
<ObjectAnimationUsingKeyFrames Storyboard.TargetName="MyImage" 
                               Storyboard.TargetProperty="HorizontalAlignment">
    <DiscreteObjectKeyFrame KeyTime="0:0:0">
        <DiscreteObjectKeyFrame.Value>
            <HorizontalAlignment>Center</HorizontalAlignment>
        </DiscreteObjectKeyFrame.Value>
    </DiscreteObjectKeyFrame>
</ObjectAnimationUsingKeyFrames>
Below is my example, where the image appears in the role of the Label:
<Grid>
    <Grid.Triggers>
        <EventTrigger SourceName="MoveToCenter" RoutedEvent="Button.Click">
            <BeginStoryboard>
                <Storyboard>
                    <ObjectAnimationUsingKeyFrames Storyboard.TargetName="Test" 
                                                   Storyboard.TargetProperty="HorizontalAlignment">
                        <DiscreteObjectKeyFrame KeyTime="0:0:0">
                            <DiscreteObjectKeyFrame.Value>
                                <HorizontalAlignment>Center</HorizontalAlignment>
                            </DiscreteObjectKeyFrame.Value>
                        </DiscreteObjectKeyFrame>
                    </ObjectAnimationUsingKeyFrames>
                    <ObjectAnimationUsingKeyFrames BeginTime="0:0:1"
                                                   Storyboard.TargetName="Test" 
                                                   Storyboard.TargetProperty="HorizontalAlignment">
                        <DiscreteObjectKeyFrame KeyTime="0:0:0">
                            <DiscreteObjectKeyFrame.Value>
                                <HorizontalAlignment>Right</HorizontalAlignment>
                            </DiscreteObjectKeyFrame.Value>
                        </DiscreteObjectKeyFrame>
                    </ObjectAnimationUsingKeyFrames>
                </Storyboard>
            </BeginStoryboard>
        </EventTrigger>
    </Grid.Triggers>
    <Label x:Name="Test" Content="Test" Width="300" Height="200" Background="Aqua" HorizontalAlignment="Left" />
    <Button Name="MoveToCenter" Content="MoveToCenter" Width="120" Height="30" HorizontalAlignment="Right" VerticalAlignment="Bottom" />
</Grid>