since it's an inventory system you're creating, it wouldn't need to edit employee details right? in this case I think it would be a good idea to just expose a service in your HR system for retrieving employee information needed by your inventory system. you just have to take into consideration in the design that retrieving employee info can be a slow process (since it's a web service), so avoid being chatty with the web service. it would be good to have all the info you need returned by the web service in just one call.
if you want fast access to the employee info, you can store it in a local database. but as much as possible i'll avoid this because of duplication and possible inconsistency between your local data and the real HR data.