Once you do this, most of your program shortcuts and web shortcuts should work just as well on different PCs, assuming you have the target programs and folders installed on both PCs in the same location. For example, I had no problem launching Skype, Chrome, or the local C: folder on multiple PCs synced this way, as they were all located at the same file location on the respective local hard drives. (You may find that some icons for programs won't transfer, but the shortcuts will still work.)
Any files and folders saved directly to the desktop will also sync across PCs without issue.
Windows will get confused if you try to launch a shortcut to a specific file or folder that isn't saved directly on the desktop and isn't available in the same location on both PCs, however. For example, trying to open a desktop-based shortcut to a specific file that's actually located in your Documents folder wouldn't work on a PC other than the computer that particular file is actually stored on. (You could move your entire Documents folder to the desktop to alleviate that issue, however.)
Syncing your Desktop to SkyDrive can also cause a little... weirdness from time to time. In my tests, my desktop icons would appear in the middle of my secondary monitor after rebooting. But that's a pretty specific problem and nothing you can't fix with a quick right-click on the desktop and selecting Sort by>Name/Size/Item type/Date Modified.
Enjoy taking your desktop anywhere and everywhere!
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