Microsoft integrated its SkyDrive file synchronization and hosting service into the Window 8.1 operating system in a way that it is enabled automatically for users signing in to the system with a Microsoft Account.
Local account users on the other hand -- those users who prefer to not use a Microsoft Account -- cannot use the implementation and are also not allowed to make use of the official SkyDrive application as it simply won't install on Windows 8.1.
Guide: See Tutorial on How to access SkyDrive on Windows 8.1
Additional Notes
I found this Tutorial very useful for accessing my other Microsoft account with 25GB SkyDrive storage space, that I cannot currently view from the File Explorer / SkyDrive folders. It has saved me the hassle of creating a new user account within Windows 8.1.
There are some benefits of using this method, as follows:
Advantage
+ Add files and folders without receiving an error of uploading an empty folder, example, when uploading an Artist with only an Album folder inside.
Disadvantage:
- Access to view or transfer files may be slow.
Deleting files/folders:
File Explorer will warn you that the deletion is a permanent action, which is partially true as they're not recoverable from your Computer's HDD. However, if you can access the Recycle Bin from your web browser, you may be able to restore the data.