According to Extended selection,
The SelectedIndex, SelectedItem, and SelectedItems properties are synchronized. For example, if you set SelectedIndex to -1, SelectedItem is set to null and SelectedItems is empty. And if you set SelectedItem to null, SelectedIndex is set to -1 and SelectedItems is empty. In multi-select mode, SelectedItem contains the item that was selected first, and Selectedindex contains the index of the item that was selected first.
Or you can use the ListViewBase.DeselectRange(ItemIndexRange) Method.