Depending on the type of legend item you want to customize, you can redefine the LegendItemTemplate and/or the LayerTemplate and/or the MapLayerTemplate.For example to redefine the lower level of legend item (the level with a swatch and a label) you can redefine the LegendItemTemplate with XAML code like:<esri:Legend Map=.........>
  <esri:Legend.LegendItemTemplate>
    <DataTemplate>
      <StackPanel Orientation="Horizontal">
        <Image Source="{Binding ImageSource}" HorizontalAlignment="Center" VerticalAlignment="Center"
          Stretch="None" MinWidth="20" />
        <TextBlock Text="{Binding Label}" Margin="5,0,0,0" VerticalAlignment="Center" />
      </StackPanel>
   </DataTemplate>
  </esri:Legend.LegendItemTemplate>
</esri:Legend>