In addition to the useful ideas in the earlier posts:
Make a backup. At least if your boss does manage to get back in you can restore things to a recent working state.
Make sure that all administrators change their passwords too. One of themmight have been compromised. Ditto for your routers, firewalls and other managed network appliances. Rename the administrator account. Check for unknown accounts. Check membership in privileged groups, you can sneak an ordinary looking user intoadministrators, backup...
You might want to create a checklist of things to do *while you boss is in the office getting fired*. This is the time to change passwords, restrict accounts, etc. Depending on the situation, if the boss gets wind of abig security sweep and he's not part of it, he might get suspicious. If he is part of it he'll be aware of the new passwords and such (bad idea).
If you're really paranoid, set working hours on accounts and set accounts to logout when their hours expire. It's amazing what you can usually do with a normal account and no supervision.
Turn on full auditing. You will probably generate lots of logs. If something does happen you can turn the data over to your legal staff. If nothing happens, after a while you can set auditing to normal levels.
Turn on and check your firewall logs. Check the firewall rules to make sure they still implement your security policy. Some firewalls have time-based rules. Consider severely restricting access except during working hours.
If your boss has a sympathetic administrator it is possible that they will work together to breach your system. This is why auditing, review and time-restricted access are necessary. You have to trust someone but the principal of "least privilege" should always be applied.
Good Luck