Using a Block's visibility setting of Show block on specific pages: Pages on which this PHP code returns TRUE (experts only)...
...what PHP would I write that returns TRUE
so that the block only shows on "Page Not Found" pages?
Can I recommend not doing it with PHP?
I would suggest making a page (via Admin->Content->Add Content), this assumes that you have the node module installed.
And then set that page as your "Default 404 (not found) page" in Admin->Configuration->System->Site Information
And then you can use that page's path in the block set up, but list under "Only the listed pages"
menu_set_active_item($path);
and $return = menu_execute_active_handler($path, FALSE);
using the 404 path you have set in config - and I thought blocks are also invoked from this. So with your 404 page set, your should be able to do compare your 404 path with menu_get_active_trail();
with php