If you have a firewall you should be able to block anything you want. Just remember though that if they can't visit anything they can't run Windows updates and such...
As Rob said, a firewall would be the best solution to accomplish this task. Though, if your company is running a domain you could also look into using Group Policy.
- How to restrict internet access Domain wide or for a single Site or OU with Group Policies
On individual PC's, if the IP configuration has no default gateway, users can access your network, but not the internet. You can create a host file for your website if needed.
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