Yes, you can run two or more instances of Skype on a PC for separate user accounts. For the first instance of Skype, log in using one user 10,
Ensure that your PC has at least two user accounts. Now right-click on the Skype icon and click on "Run as".
In the dialog box that opens, click on the radio button next to "The following user", and in the drop-down box, select the username with which you would like to log into Skype. Another instance of Skype will open up which you can use independent of the first instance.
Now, follow these steps to customize the Skype icon so that as soon as you click on it, a pop up asks you to specify the user account that you would like to log into.
o Right-click and select "Properties", and under the "Shortcut" tab, click on the "Advanced" button,
o In the "Advanced Properties" dialog box, insert a check mark near the option "Run with different credentials". o Click "OK" twice to apply the settings,
Now as soon as you click on this Skype icon, the "Run as" dialog box will pop up asking you which account you would like to use to run Skype. To make things even simpler for different users and to avoid confusion, use another icon for this shortcut.
Even though you sign out of Skype, you'll notice that your Skype 10 still remains in the user 10 field. In case you share your PC at work with one or more users, for example, if you sign into Skype at an Internet cafe or a multi-user PC at work, then you might want to remove your Skype 10 from this field so that other users don't get to know your 10. Follow these steps to remove your Skype 10 from the user 10
Under "The following user", select the username that you would like to use to si n into Skype. field after you've logged out.
Navigate to this directory: C:\ Documents and Settings\IUsernamel\ Application Data\Skype. Browse to the folder with your 10, and take a backup of the folder in case you would like to retain the history of your conversations.
Now delete the folder with your Skype ID.