To use more than one Skype account on the same computer at the same time you need to start a new instance of Skype.
Click Start > Run (or press the Windows and R keys on your keyboard at the same time)
In the Run window, enter the following command (include the quotes) and press OK:
“C:\Program Files\Skype\Phone\Skype.exe” /secondary
If this solution fails, you can try another option:
Tags: General Tips, Skype, Tips, Two Account in one computer.