If you’re familiar with the personal cloud storage service you get with SkyDrive, you’ll be right at home with SkyDrive Pro, a service optimized for business and managed by your company or organization. It’s your hub for work
documents: the one place to find, store, and share the files you care about for work.

Syncing SkyDrive Pro with your local desktop is very easy (for this tutorial, I am using SharePoint 2013 - Consumer Preview, online):-

1) Click on the SkyDrive link on the top bar

 

2) Once your document library loads, click on the Sync button

3) Give permissions to the below popup

4) You can go with the default values for SharePoint library and Desktop Folder and Click on Sync Now

5) Choose the suitable option from the below

6) Enter your credentials below and Sign In

7) You will soon see your SkyDrive folder synced with your desktop's specified folder.

Enjoy your important documents offline accessible from your PC, Phone & Tablet.

The above just serves as a broad guideline hence please try it in test environment before implementing in Production!