Add this code to function.php, the customer username will show on your admin woocommerce customer order detail
add_action( ‘woocommerce_admin_order_data_after_billing_address’, ‘woo_display_order_username’, 10, 1 );
function woo_display_order_username( $order ){
global $post;
$customer_user = get_post_meta( $post->ID, ‘_customer_user’, true );
echo ‘‘.__(‘Customer Username’).’: ‘ . get_user_meta( $customer_user, ‘nickname’, true ) . ‘
‘;
}