Summary: My Documents, Username's Documents and the My Documents folder in the Documents and Settings folder all relate ... intimately.
In "My Computer," I have a folder "My Documents" - 12.9 GB, 11.7 GB size on disk. I also have a folder "Robert and Brenda's Documents" - 12.9 GB, 11.7 GB size on disk. Then there is a folder "C:\Documents and Settings\Robert and Brenda\My Documents" - 12.9 GB, 11.7 GB on disk.
Am I actually using roughly 36 GB for these? And, if so, what if any of these, can I safely delete?
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Windows is trying to be helpful, and in the process is being slightly confusing as well.
If you look closely at the contents of those three folders you'll find that they're strikingly similar. Identical even.
And that would be our clue.
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Here are two of the three culprits as shown on my machine in Windows Explorer:

And of course, like you, I have "C:\Documents and Settings\LeoN\My Documents" as well.
By now you've probably guessed: three names for the exact same thing.
So, no, in your case you're not taking up 36 gigabytes, it's only the single 12.9 gigabytes being reported in three different places. Delete something in one place and you'll see it disappear from all three.
Why?
Good question. As I said, it's Windows trying to be helpful.
"C:\Documents and Settings\LeoN\My Documents" is the official and correct location for the folder, but it's also cumbersome.
"My Documents" is a convenient shortcut, nothing more. In fact, it's something that programs can count on, so that they don't have to know that when they're on your machine it's "Robert and Brenda", and on mine it's "LeoN". They can just reference "My Documents", and they'll get the correct folder for the currently logged in user.
"LeoN's Documents" is a little harder to rationalize, but on a system with multiple user accounts, each would likely have a named shortcut so that files could easily be exchanged as desired between users.
Related:
Where is Windows Explorer? Windows Explorer is everywhere - yet finding Windows Explorer on the Start Menu is actually fairly difficult. We look at where Windows Explorer is, and some of the many other ways you can get to it.
How can I get Windows Explorer to default to open on a directory of my choosing? You can create a shortcut to open Windows Explorer on the directory of your choice.
How do I get Windows Explorer to display details by default? Windows Explorer defaults to a simple view of the files on your machine. You can change that default to include all details by following a few steps.
Article C3642 - February 7, 2009
It is also possible to redirect where Windows XP sends 'My Documents'. I prefer to partition my Drive and store Data on drive E: . To do this, right-click on the My Documents folder and select properties. Here you can change the Target Location folder. You can also change the Store folder for your Outlook Express e-mail messages to your data drive as well. ( Tools > Options > Maintenance tab > Store Folder.
This has the advantage that if I get a pesky hard-to-get-rid-of virus or malware, I can easily restore my C: drive image and not lose any recent documents.
I have not figured out how to redirect the Address book nor Favorites, so simply copy them to the E: drive occasionally.
Posted by: Jake Smith at February 10, 2009 9:28 AM"E" drive is the folder that you have ready to burn to a cd. Why would you you send folders to that place to store them?
Posted by: James King at February 10, 2009 7:51 PMIf his HDD originally only had one partition on it, his optical drive would be D:, making his newly added partition E:
Posted by: Walter McMurry at February 11, 2009 5:14 PMI normally set a hard drive up with 5 or 6 partitions. C for the operating system, D for the program files, E for Data, F for photos and G for back-up images.
BY the way, Leo explains a much easier method to change the location of the "My Documents" folder.
search Leo's database for " change my Documents location "
Posted by: Jake Smith at February 17, 2009 8:01 PM