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While logged out, visit that site and click on the "Help, I can't log in" button and then follow the steps.
These will tell him if the hijacker is trying to get control of his account by locking him out, they probably have changed the email address associated with the account by now. They can't however change the username of the account and this is what you will need to use in your support request to steam along with some proof you own the account, things like purchase orders (these can be found in his email by seaching for "steam purchase").
Stolen/hijacked steam account https://support.steampowered.com/kb_article.php?ref=2347-qdfn-4366
Account security recommendations https://support.steampowered.com/kb_article.php?ref=1266-OAFV-8478