If they already have a system for the use of it, you should have no problems.
If they haven't used it and just decided that they want to start ... it can be a nightmare.
Dreamweaver is a great tool, but like a lot of software it considers itself to be your end all and be all of your web production. It just LOVES to pepper your folders with hidden junk unless you tell it not to.
I am still stumbling across old check in/out files, even though I stopped using it after DW 4.0. Unless you exclusively restrict ALL company wide web file creation, editing, upload and download you will still be able to modify any files, without being locked out, regardless whether the file is checked out by someone acording to DW. So, you can have people quick editing files in notepad, or any other editor, using a plain ftp, and the file will be changed even though it is "checked out" by someone.
And unless you are all very strict about checking back in, you will quickly discover people sitting on checked out files for days or weeks until reminded to check it back in. But what if, in the meantime, you already modified the file?
Unless you have very strict rules about who can work on what and for how long, confusion will reign.
Also, for security, I HIGHLY recommend turning off auto generate "Notes". If your folder is compromised and it has DW Notes in it, an intruder can gather information about your files.
Don't let DW "auto" anything when it comes to getting or putting on the server.